LT3867B - Acrylic acid derivatives - Google Patents

Description

The present invention relates to acrylic acid derivatives useful as fungicides, to processes for their preparation, to fungicidal compositions containing these derivatives, and to methods for controlling fungi, in particular fungal infections of plants, by their use.

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

and stereoisomers thereof wherein X, Y and Z, which may be the same or different, are hydrogen or halogen, or optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl, optionally substituted alkynyl, haloalkyl, alkoxy, haloalkoxy, optionally substituted aryloxy , optionally substituted arylalkoxy, optionally substituted acyloxy, optionally substituted amine, optionally substituted arylazo, acylamine, nitro, nitrile, -CO ₂ R ³ , -CONR ⁴ R ⁵ , -COR ⁶ , -CR ⁷ = NR ⁸ or -N = CR ⁹ R ¹⁰ groups, or X and Y groups, when adjacent to the phenyl ring, may be bonded together to form a fused ring, aromatic or aliphatic, optionally containing one or more heteroatoms; and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ , which may be the same or different, are hydrogen or alkyl, cycloalkyl, alkenyl, alkynyl, optionally substituted aryl, optionally substituted aralkyl, or cycloalkylalkyl; and its metal complexes.

The compounds of the invention have at least one carbon-carbon double bond and are sometimes obtained in the form of geometric mixtures of isomers. However, these mixtures may be resolved into individual isomers and the present invention includes such isomers.

Alkyl groups may be in the form of linear or branched chains and preferably have from 1 to 6 carbon atoms; examples are methyl, ethyl, propyl, (n- or iso-propyl) and butyl (n-, sec-. iso-or t-butyl). The methyl group is a more preferred alkyl group because of R ¹ and R ² .

According to another aspect of the invention there are provided compounds having the general formula O):

and stereoisomers thereof wherein X, Y and Z, which may be the same or different, are hydrogen or halogen, or optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl, optionally substituted alkynyl, haloalkyl, alkoxy, haloalkoxy, optionally substituted aryloxy , optionally substituted arylalkoxy, amine, acylamine, nitro, nitrile, -CO ₂ R ³ , -CONR ⁴ R ⁵ or -COR ⁶ groups; and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ , which may be the same or different, are hydrogen or alkyl, cycloalkyl, alkenyl, alkynyl, optionally substituted aryl, optionally substituted aralkyl or cycloalkylalkyl; and their metal complexes.

According to another aspect of the invention there are provided compounds having the general formula (I):

and stereoisomers thereof wherein X, Y and Z, which may be the same or different, are hydrogen or halogen, or optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl, optionally substituted alkynyl, haloalkyl, alkoxy, optionally substituted aryloxy, optionally substituted arylalkoxy, optionally substituted amine, -CO ₂ R ³ , -COR ⁶ groups; or groups X and Y, when adjacent to the phenyl ring, may be bonded to form a fused aromatic ring; and R ¹ , R ² , R ³ and R ⁶ , which may be the same or different, are alkyl, optionally substituted phenyl or optionally substituted aralkyl.

According to another aspect of the invention there are provided compounds having the general formula (I):

and stereoisomers thereof, wherein X, Y and Z, which may be the same or different, are hydrogen, fluorine, chlorine or bromine, or Ci. ₄ alkyl, C _2-5 alkenyl,

C _2-5 alkynyl, phenyl, Ci_ ₄ haloalkyl, Ci- ₄ alkoxy, phenoxy, benzyloxy or mono- or dialkylamino groups or groups X and Y, when they are in adjacent positions on the phenyl ring is bound, forming a fused ring aliphatic any of the moieties of the above groups being optionally substituted by one or more C _1-4 alkoxy groups, fluorine or bromine atoms, phenyl rings which are themselves optionally substituted, heterocyclic rings which are either aromatic or non-aromatic and are themselves optionally substituted, nitro, amino, nitrile, hydroxyl or carboxyl groups; and wherein the phenyl moieties of any of the above groups are optionally substituted with one or more fluorine, chlorine or bromine atoms, phenyl rings, C _1-4 alkyl, C _1-4 alkoxy, nitro, amino, nitrile, hydroxyl or carboxyl groups; and R ¹ and R ² , which may be the same or different, are C _1-4 alkyl, phenyl or benzyl, each optionally substituted by halogen.

According to another aspect of the invention there are provided compounds having the general formula (XI):

(XI) wherein R is optionally substituted phenyl or optionally substituted benzyl and Y is a hydrogen or halogen (fluorine, chlorine or bromine) atom, or a methyl, methoxyl, nitro, nitrile, carboxyl or methoxycarbonyl group.

According to another aspect of the invention there are provided compounds having the general formula (XII):

(XII) and stereoisomers thereof, wherein X is an alkyl, alkenyl, alkynyl, aryloxy or arylalkoxy group, each of which is optionally substituted.

According to another aspect of the invention there are provided compounds having the general formula (XIII):

(XIII) and stereoisomers thereof, wherein X is a group of optionally substituted alkyl, optionally substituted alkenyl or optionally substituted alkynyl.

In an individual case, the invention according to another aspect of the compounds where the optional substituents in the preceding paragraph are phenyl, itself optionally substituted with one or more of the following substituents: fluorine, chlorine, bromine, Ci- ₄ alkyl (especially methyl), C ^ alkoxy (especially methoxy) or nitro.

According to a further aspect of the present invention there are provided compounds having the general formula (XIV):

(XIV) and stereoisomers thereof, wherein X is an optionally substituted aryloxy group or an optionally substituted arylalkoxy group.

In the preceding paragraph, group X may be phenoxy or benzyloxy, each of which may be substituted by one or more halogens (fluoro, chloro or bromo), or methyl, methoxyl, ethyl, ethoxyl, nitro, nitrile, carboxyl or methoxycarbonyl.

In another aspect of the invention there is provided a compound having the general formula (XV):

and stereoisomers thereof, wherein X, Y and Z, which may be the same or different, are fluoro, chloro, bromo or hydrogen, or methyl, methoxyl or nitro.

The invention provides compounds:

1)

(Compound 9 in Table 1 below).

2)

CH ₃ O ₂ C

H (compound 13 in Table 1 below).

3)

(Compound 19 in Table 1 below).

4)

OCH ₃ (compound 1 in Table 2 below)

5)

(Compound 1 in Table 4 below) Tables 1 and 2 below.

table

c ⁺ o 2 .N LU | NI LUl LLJI LUl LUl LUl LU | LUl NI LU | LU | olefic nine * m m co cm cm co n co N oo co UO CO LO CO CO LO CO M CO UO UO UO l <CO N N N N N N N CO N N Melting point (° C) oo ω ω ω ω ω οο «ο« ο {Ο co .3 .3 .3 .3 .3 co .3 .3 h * · = ι <Ν 4 ιό c o c o c o c o o o o o o o o o v-T " N ΧΧΧΧΧΧ ΧΧΧΧΧΧ > ΧΧΧΧΧΧ ΧΧΧΧΧΧ X X X X X o o o o X X X X o o o o m m m m X X X X CO CD to {D O O O O LUl LUl UJI LLJI ΧΧΧΧΧΧ X X CM C \] oo 4 cu □ c CM CM XX co co co rr rr co <co co co co co X X X O O X X X X X X O O O I £ O ΧΟΟΟΟΟ O O ό cc CJ -p X O -L- -L- {Λ co o o 4 CO CO CO CO CO T CO 'T CO co co co X X X X X O X Λ X X X X o o o o o o o o o o o o The compound No. -r- cu co uo co s 03 cn ° INZ

ro ro .ū ro

E LU | NI LU | LUI LUI LUI LUI LUI LUI LUI LUI LUI LUI NI LUI LUI NI LU | LUI LUI 1 'c * M— CO G) '? = O r- r- 00 O CO CO V- 00 O CM LO CM CM co Q. LO n co co io LO co LO LO co LO r- CO LO LO LO LO co co t < i < N N N N N N l < co N N CO N N N CM h- r- _J Φ ' ω 3 ^ Φ ω tn 3 ro ro 3, ro r- co 1 ro 3 'ro CO CO t CM CO » 05 CO 1 1 CM 1 co ro 3 'ro O OO J ro 3 'ro CO CO ro 3 'ro co co 1 o 1 co -t— · co co LO V " co 7t CM 05 'Ro CM ro LO o ro σ> ro ro co ro CD co co ro N CO CO

N

ΧΧΧΧΧΧΧΧΧΧΧΧΧΧΧΧΧΧΧΧ

O O O O LL

ΧΧΧΧΧΧΧΧΧΧ4ώιόίόώΧΧΧΧΧ

X X X X O O O O

X X X X o o o ro in m

XXX co ro cd

O o o o

ro

X co

O

CO OJ

X Ίο O X x 52 o o

OI OI r

X X vi X

O O O o ro cn ro · X X X ~ co co JL

CNCMCMCMCMCMCMCMCNtTCMCMCDCO co

X

O

OJ

co X o co X o O o co LL O X <O O CM CM CM CM CM

OJ cc o

co co co

XXX co co _T cococococococococococococococococo _n xxxxxxxxxxxxxxxx OūOiiOOOOOOOOOOOOOOOO sequel) cc o

co _ CO co co -r * cocococococococococococococococococo χχΛχχχχχχχχχχχχχχχχχ ooLiooooooooooooooooo

CO ^ tiOCOI ^ -COCOO-r-CMCO'ctlOCOl ^ -OOCDOT-CM

T-i-T-T-T - r-r-CJ (N (NWO4 (NWCUWWC0nn

C ⁵ ° ~ 3

isomer ⁴ · LLII LJJt LU | LU | LU | LU | LUl LLJ | LU | LU | LUl LUl LXJ | UJ | LUl IU | olefinic nis * 1 Π3 c Φ o co o 5 'F? co šT lo o J2 b- 'FA CO ^- 4 = Lyd. temp. (° C) Ω ω w m 3 = 5 Σ3 . 'Φ φ φ oo Φ co N ΧΧΧΧΧΧΧΧΧΧΧΧΧ ΧΧΧΧΧ > ΧΧΧΧΧΧΧΧΧΧΧΧΧ ΧΧΧΧΧ

O CM <M X X X O CO O CM o X X CM X o co X o O ω _ęC X o 't X CD O CM X CD O 1 X co o CM -T— X o X o O CM o O CM CM O o to Φ <N X 'St X to o t o CO X t · \ o X X X CM co o ό X o o X LO o LO o to o LO O LO co co that _o o m o co X o LO o LO X LO X (\ co X CM o X X X X X X 2 «; X o o X X ~ i o co to o to o co o to o to o o Ό co O to o to O X X to X o S- X o CM CM CM cb cb cb cb cb cb cb cb cb cb cb cb CM CM 1 CM

cc cocococococococococococococo

ΧΧΧΧΧΧΧΧΧΧΧΙΤ oooo. ooooooooo

CO CO CO CO CO

ΧΧΧΧΧ o o o o o (continued) cc

COCOCOCOCOCOCOCOCOCOCOCOCO

ΧΧΧΧΧΧΧΧΧΧΧΧΧ ooooooooooooo c ⁵ .2 O 'c co'i-incob-coOTOT-ojco'tLn ηωηωηωω ^^' ίτττ} · ^ ω n ω ω o

W- Table W (cont'd)

iso- mayor * LLII LLJI LLJI LU | llll NI LU | LU | NI olefinic nis * 1 1 CO CO c (D c CD -f- t -. T - CO CO TT ¹⁰ 2 2 ^1X1 LO LO CO l <CO + = CO '4 = N CD NN CD Lyd. temp. (° C) O CO - cn cn cn cn „cn o.o V _® .2, .2, m .2, φ CD N>, φ N 'φ ι' φ = - 'd- dd. - O N - co co t- cn co -i— co cn co N T T T T T T T T T T t t x t t t t x r X I T o o i i o o CM r = k F = k 5 o o ą; ω ω ω,, and O O co LO LO LO nu III LO LO LO χ χ x x B ta t t t Z Λ CO CO <O Λ | Λ. CO CO CO., LTD O O o o o o o III III CN CN Cd CN CO M- CM □ C co co co co co co co co T T T X X X X X X X ooo o o o o o o o CC cococo co co co cococo XXX X X X XXX ooo o o o ooo Jung nio No. t- w n Tt lo cd r- oo cn Lf) LD LD LD LD LO LO IDLDLD

isomers ⁺ i LUI tnl UJI LU | U-H (Λ C 'C * h- CO co "Ω co o r < rJ £ ± E m co ω O ~ o CM CM v " V " • a 1 co CM >> CM co CM oo Ύ—

table (continued)

N T Z Z z Z > - ___ __. , __ ._. * -c * * * X * * * * * CM CC co co co co co z Z T z z o o o o o CC co co co co co Z Z Z z z O O o o o 5? o c § c 2 O ΤΓ- CM co —I co co co co co

you

1 - c

* O) c

CM

CD <0

W>.

C 'm c

D

CD

table (continued)

iso- mayor '*' (JJl LUI LUI LU | LUI LU | LUJ L £ J | LU | olefinic nis * aromatic in teak 7.32 To I Lyd. temp. (° C) oil oil I I N X ΧΧΧΧΧ ΧΧΧΧ > X ΧΧΧΧΧ ΧΧΧΧ X ί 'ib O. £ XXO OX -r ¹ O _ £? O _ For this S i XO o T f ω XO o .χ ^ -į oo .4 O £ θΟθΓ- \ θώώ = ξ, xo ITT> 4 4 cm 0 O b O Ο O LLJI LLJl LLJJ LhJl CM CM CM CM CM CM CM CM CM CM CM CC CO CO CO CO CO CO CO CO CO CO CO X ΧΧΧΧΧ ΧΧΧΧ o 00000 0000 CC CO CO CO CO CO co co co co co X ΧΧΧΧΧ ΧΧΧΧ o 00000 0000 Jung nio No. lo ω n oo cn 0 t- cm co co co co co r-

table (continued)

- Goat mayor ⁺ LU | UJl UJl Nl Nl LU | LLtl LLJ | UJI UJI C * ω ω c o no E OJ o o >, N T Z Z Z Z Z Z Z Z z > Z z z Z Z z z z Z z CM z co co ' X o z o .__ o X X cu X X X co X o o o See co o CM o o o o LO T co o X X o z X _L z o LO Z to o o F co o = k _V) OJ z o o LO z z o o uO z o o o m X Z o o LO Z o & O t UJl yeah UJI LLA co o co o co o co o LLJ1 ώ OJ OJ 01 CM OJ oh OJ OJ CM CM CM CC CO CO co co CO CO CO CO CO co T z z z z z z z z z o o o o o o o o o o cc co co co co co co co CO co co z z z z z z z z z z o o o o o o o o o o c Σ3 o c Έ 2 IO co r-- co Oops o OJ oo Etc. "3 r- r- r- N 00 00 co co co

table (continued)

iso- mayor * LUl UJ | LUl LUl LU | LUl olefinic nis * aromatic in teak Lyd. temp. (° C) i 1 99-100 I N X XX XXX > X XX XXX X X XX χ q Z ° KP xz 8 8 oooox? V 7 - γΛ ° ^{z z} X () XX ° yjt ooo _ 1 --- '1 i · 1 04 C \ J C4 C \ j 04 04 CM tr co co co co co X XX X XX o o o o o o o cc <0 co co co co X XX XXX O O O O O O Jung nio No. LO CO N 00 O) O oo oo oo oo oo m

O c

'Ow)

Φ

E

0)

O

C

X3 £

3? • '{D

CL k_ co o

4- »pig

-id o

Q>

E

I

4-CD _Q

O

C

Oh o

cl o

c 'c jd o

o

C co be c

w

O

CL

O «♦ - ¹ J) cn c

'Co co' c

E

No. 0)

p

Q.

Oh to

ΞΕ 'cl + Geometry of the beta-methoxyacrylate group.

table

RO co ₂ ch ₃

CH

OCH ₃

The compound No. R Melting temp. (° C) olefinic * isomers * 1 c ₆ h ₅ oil 7.47 Ę 2 2-FC ₆ H ₄ E 3 3-FC ₆ H ₄ Ę 4 4-FC ₆ H ₄ 77-78 7.50 E 5 2-CI-C ₆ H ₄ oil 7.46 Ę 6th 3-CI-C ₆ H ₄ oil 7.45 E 7th 4-CI-C ₆ H ₄ oil 7.48 Ę 8th 2-Br-C ₆ H ₄ E 9th 3-Br-CeH ₄ Ę 10th 4-Br-C ₆ H ₄ Ę 11th 2 -C ₆ H ₄ Ę 12th 3 -C ₆ H ₄ E 13th 4 -C ₆ H ₄ E

table (continued)

The compound No. R Melting temp. (° C) olefinic * treasury m er ⁺ 14th 2-CH ₃ -C ₆ H ₄ E 15th 3-CH ₃ -C ₆ H ₄ Ę 16th 4-ΟΗ ₃ -ΟθΗ ₄ 80-81 7.50 E 17th 2-CH ₃ CH ₂ -C ₆ H ₄ Ę 18th 3-CH ₃ CH ₂ -C ₆ H ₄ E 19th 4-CH ₃ CH ₂ -C ₆ H ₄ E 20th 2- (CH ₃ ) ₂ CH-C ₆ H ₄ Ę 21st 3- (CH ₃ ) ₂ CH-C ₆ H ₄ Ę 22nd 4- (CH ₃ ) ₂ CH-C ₆ H ₄ Ę 23rd 2- (GH ₃ ) ₃ CC ₆ H ₄ Ę 24th 3- (CH ₃ ) ₃ CC ₆ H ₄ E 25th 4- (CH ₃ ) ₃ CC ₆ H ₄ Ę 26th 2-CH ₃ OC ₆ H ₄ E 27th 3-CH ₃ OC ₆ H ₄ Ę 28th 4-CH ₃ OC ₆ H ₄ oil 7.51 Ę 29th 2-CF ₃ OC ₆ H ₄ E 30th 3-CF ₃ OC ₆ H ₄ Ę 31st 4-CF ₃ OC ₆ H ₄ Ę

table (continued)

The compound No. R Melting temp. (° C) olefinic * isomers ⁺ 32 2-C6H5O-C6H4 E 33 3-C6H5O-C6H4 Ę 34 4-C6H5O-C6H4 E 35 2-NO2-C6H4 E 36 3-NO ₂ -C ₆ H ₄ Ę 37 4-NO2-C6H4 Ę 38 2-NH ₂ -C ₆ H ₄ Ę 39 3-NH ₂ -C ₆ H ₄ Ę 40 4-NH ₂ -C ₆ H ₄ E 41 2-C6H5-C6H4 E 42 3-C6H5-C6H4 E 43 4-C6H5-C6H4 Ę 44 2-HO ₂ CC ₆ H ₄ Ę 45 3-HO ₂ CC ₆ H ₄ Ę 46th 4-HO ₂ CC ₆ H ₄ Ę 47 2-CH ₃ O ₂ CC ₆ H4 E 48 3-CH3O2C-C6H4 Ę 49 4-CH3O2C-C6H4 Ę

table (continued)

The compound No. R Melting temp. (° C) olefinic * isomers * 50 2- (CN) -C ₆ H ₄ E 51 3- (CN) -C ₆ H ₄ E 52 4- (CN) -C ₆ H ₄ Ę 53 2-HO-C ₆ H ₄ E 54 3-HO-C ₆ H ₄ Ę 55 4-HO-C ₆ H ₄ E 56 2-CH ₃ C (O) NH-C ₆ H ₄ E 57 3-CH ₃ C (O) NH-C ₆ H ₄ E 58 4-CH ₃ C (O) NH-C ₆ H ₄ E 59 2,3-di-FC ₆ H ₃ E 60 2,4-di-FC ₆ H ₃ Ę 61 2,5-di-FC ₆ H ₃ Ę 62 2,6-di-FC ₆ H ₃ Ę 63 3,4-di-FC ₆ H ₃ Ę 64 3,5-di-FC ₆ H ₃ Ę 65 2,3-di-Cl-C ₆ H ₃ Ę 66 2,4-di-Cl-C ₆ H ₃ oil 7.48 Ę 67 2,5-di-Cl-C ₆ H ₃ E

table (continued)

The compound No. R Melting temp. (° C) olefinic * isomers ⁺ 68 2,6-di-Cl-C ₆ H ₃ 132-133 7.62 Ę 69 3,4-di-Cl-C ₆ H ₃ E 70 3,5-di-Cl-C ₆ H ₃ Ę 71 2,3-di-CH ₃ -C ₆ H ₃ Ę 72 2,4-di-CH ₃ -C ₆ H ₃ Ę 73 2,5-di-CH ₃ -C ₆ H ₃ E 74 2,6-di-CH ₃ -C ₆ H ₃ Ę 75 3,4-di-CH ₃ -C ₆ H ₃ Ę 76 3,5-di-CH ₃ -C ₆ H ₃ Ę 77 2,3-di-CH ₃ OC ₆ H ₃ Ę 78 2,4-di-CH ₃ OC ₆ H ₃ Ę 79 2,5-di-CH ₃ OC ₆ H ₃ E 80 2,6-di-CH ₃ OC ₆ H ₃ E 81 3,4-di-CH ₃ OC ₆ H ₃ E 82 3,5-di-CH ₃ OC ₆ H ₃ Ę 83 2-F, 3-CI-C ₆ H ₃ Ę 84 2-F, 4-CI-C ₆ H ₃ E 85 2-F, 5-CI-C ₆ H ₃ Ę

table (continued)

The compound No. R Melting temp. (° C) olefinic * isomers * 86 2-F, 6-CI-C ₆ H ₃ Ę 87 3-F, 4-CI-C ₆ H ₃ Ę 88 3-F, 5-CI-C ₆ H ₃ Ę 89 2-CI, 3-FC ₆ H ₃ E 90 2-CI, 4-FC ₆ H ₃ Ę 91 2-CI, 5-FC ₆ H ₃ E 92 3-CI, 4-FC ₆ H ₃ Ę 93 2-F, 3-CH ₃ -C ₆ H ₃ Ę 94 2-F, 4-CH ₃ -C ₆ H ₃ E 95 2-F, 5-CH ₃ -C ₆ H ₃ Ę 96 2-F, 6-CH ₃ -C ₆ H ₃ E 97 3-F, 4-CH ₃ -C ₆ H ₃ E 98 3-F, 5-CH ₃ -C ₆ H ₃ E 99 2-CH _3i 3-FC ₆ H ₃ Ę 100 2-CH _3i 4-FC ₆ H ₃ E 101 2-CH _3j 5-FC ₆ H ₃ E 102 3-CH ₃ , 4-FC ₆ H ₃ Ę 103 2-F, 3-CH ₃ OC ₆ H ₃ E

table (continued)

The compound No. R Melting temp. (° C) olefinic * isomers * 104 2-F, 4-CH ₃ OC ₆ H ₃ Ę 105 2-F, 5-CH ₃ OC ₆ H ₃ Ę 106 2-F, 6-CH ₃ OC ₆ H ₃ E 107 3-F, 4-CH ₃ OC ₆ H ₃ E 108 3-F, 5-CH ₃ OC ₆ H ₃ Ę 109 2-CH ₃ O, 3-FC ₆ H ₃ Ę 110 2-CH ₃ O, 4-FC ₆ H ₃ E 111 2-CH ₃ O, 5-FC ₆ H ₃ Ę 112 3-CH ₃ O, 4-FC ₆ H ₃ Ę 113 2-Cl, 3-CH ₃ -C ₆ H ₃ E 114 2-Cl, 4-CH ₃ -C ₆ H ₃ Ę 115 2-Cl, 5-CH ₃ -C ₆ H ₃ Ę 116 2-Cl, 6-CH ₃ -C ₆ H ₃ Ę 117 3-Cl, 4-CH ₃ -C ₆ H ₃ E 118 3-Cl, 5-CH ₃ -C ₆ H ₃ E 119 2-CH ₃ , 3-CI-C ₆ H ₃ Ę 120 2-CH ₃₎ 4-CI-C ₆ H ₃ Ę 121 2-CH _3i 5 -Cl-C ₆ H ₃ Ę

table (continued)

The compound No. R Melting temp. (° C) olefinic * isomers * 122 3-CH ₃ , 4-CI-C ₆ H ₃ Ę 123 2-CI, 3-CH ₃ OC ₆ H ₃ Ę 124 2-CI, 4-CH ₃ OC ₆ H ₃ Ę 125 2-CI, 5-CH ₃ OC ₆ H ₃ Ę 126 2-CI, 6-CH ₃ OC ₆ H ₃ Ę 127 3-CI, 4-CH ₃ OC ₆ H ₃ E 128 3-CI, 5-CH ₃ OC ₆ H ₃ Ę 129 2-CH ₃ O, 3-CI-C ₆ H ₃ Ę 130 2-CH ₃ O, 4-CI-C ₆ H ₃ Ę 131 2-CH ₃ O, 5-CI-C ₆ H ₃ E 132 3-CH ₃ O, 4-CI-C ₆ H ₃ E 133 2-CH _3j 3-CH ₃ OC ₆ H ₃ E 134 2-CH ₃ , 4-CH ₃ OC ₆ H ₃ Ę 135 2-CH _3i 5-CH ₃ OC ₆ H ₃ E 136 2-CH _3i 6-CH ₃ OC ₆ H ₃ E 137 3-CH ₃ , 4-CH ₃ OC ₆ H ₃ E 138 3-CH ₃ , 5-CH ₃ OC ₆ H ₃ E 139 2-CH ₃ O, 3-CH ₃ -C ₆ H ₃ Ę

table (continued)

The compound No. R Melting temp. (° C) olefinic * isomers * 140 2-CH ₃ O, 4-CH ₃ -C ₆ H ₃ Ę 141 2-CH ₃ O, 5-CH ₃ -C ₆ H ₃ Ę 142 3-CH ₃ O, 4-CH ₃ -C ₆ H ₃ E 143 2,4,6-tri-FC ₆ H ₂ Ę 144 2,4,6-tri-Cl-C ₆ H ₂ E 145 2,4,6-tri-CH ₃ -C ₆ H ₂ E 146 2,6-di-F, 4-CI-C ₆ H ₂ Ę 147 2,6-di-Me, 4-FC ₆ H ₂ Ę 148 2,6-di-Cl, 4-FC ₆ H ₂ Ę 149 2,3,5,6-tetra-Cl-CeH E 150 Pentafluorophenyl E 151 Pentachlorophenyl E 152 H E 153 ch ₃ oil 7.52 Ę 154 ch ₃ ch ₂ E 155 ch ₃ ch ₂ ch ₂ E 156 (CH ₃ ) ₂ CH E 157 ch ₃ ch ₂ ch ₂ ch ₂ Ę

table (continued)

The compound No. R Melting temp. (° C) olefinic * isomers * 158 (CH ₃ ) ₃ C Ę 159 Cyclohexyl oil 7.38 E 160 CH ₂ : CHCH ₂ oil 7.46 Ę 161 Ę-C ₆ H ₅ CH: CHCH ₂ oil 7.46 E 162 CH ₂ : C (CH ₃ ) CH ₂ E 163 E-CH ₃ CH: CHCH ₂ E 164 2-tetrahydropyrinyl E 165 2-pyridyl oil 7.43 Ę 166 3-pyridyl E 167 4-pyridyl Ę 168 2- (5'-CF ₃ -pyridyl) Ę 169 2-pyrimidyl Ę 170 4-pyrimidyl Ę 171 5-pyrimidyl Ę 172 3,4-methylenedioxyphenyl E 173 1-naphthyl Ę 174 2-naphthyl E

table (continued)

The compound No. R Melting temp. (° C) olefinic * isomers * 175 ch ₃ sch ₂ E 176 c ₆ h ₅ sch ₂ Ę 177 c ₆ h ₅ ch ₂ 76-77 7.49 Ę 178 C ₆ H ₅ C (CH ₃ ) ₂ E 179 4-CI-C ₆ H ₄ C (CH ₃ ) ₂ E 180 ch ₃ 74-75 6.55 Z 181 c ₆ h ₅ oil 6.60 Z

+ Chemical shift of the singlet from the olefinic proton in the betamethoxyacrylate group (md from tetromethylsilane) Solvent: CDCI ₃ * Beta-methoxyacrylate group geometry.

The following table covers compounds of the general formula:

wherein the group R includes all the groups R listed in Table 2 for each of the substituents, exemplified in the phenyl ring, listed above. The acrylate group in each case may have either E- or Z- geometry in the table

Y Z 3-F H 4-F H 5-F H 6-F H 3-CI H 4-CI H 5-CI H 6-CI H 3-CHg H 4-CH ₃ H 5-CH ₃ H 6-CH ₃ H 3-NO ₂ H 4-NO ₂ H

Y Z 5-NO2 H 6-NO2 H 5-CF3 H 3-NO2 5-CI 3-NO2 5-NO2 5-SCH3 H 4-CH3O 5-CH3O 4- (CH ₃ ) ₂ N H 4,5-methylenedioxy

Specific examples of this type of compound shown in Table 3 are:

Compound No. R Y Z Lyd. temp. (° C) Olefin * Isomers * 1 c ₆ h ₅ 3-CI H Ę 2 c ₆ h ₅ 4-NO ₂ H Ę 3 c ₆ h ₅ 5-CI H oil 7.47 E 4 c ₆ h ₅ 6-NO2 H Ę 5 c ₆ h ₅ 5-NO2 H oil 7.60 Ę

* Chemical shift of the singlet from the olefinic proton in the beta-methoxyacrylate group (da. from tetramethylsilane).

Solvent: CDCI ₃ .

⁺ Beta-methoxyacrylate group geometry.

table co ₂ ch ₃

The compound No. R Melting temp. (° C) olefinic * isomers ⁺ 1 c ₆ h ₅ oil 7.59 Ę 2 2-FC ₆ H ₄ Ę 3 3-FC ₆ H ₄ E 4 4-FC ₆ H ₄ Ę 5 2-CI-C ₆ H ₄ Ę 6th 3-CI-C ₆ H ₄ E 7th 4-CI-C ₆ H ₄ Ę 8th 2-Br-C ₆ H ₄ E 9th 3-Br-CeH ₄ Ę 10th 4-Br-CeH ₄ Ę 11th 2 -C ₆ H ₄ E 12th 3 -C ₆ H ₄ Ę 13th 4 -C ₆ H ₄ E

table (continued)

The compound No. R Melting temp. (° C) olefinic * isomers ⁴ 14th 2-CH ₃ -C ₆ H ₄ E 15th 3-CH ₃ -C ₆ H ₄ E 16th 4-CH ₃ -C ₆ H ₄ Ę 17th 2-CH ₃ CH ₂ -C ₆ H ₄ E 18th 3-CH ₃ CH ₂ -C ₆ H ₄ E 19th 4-CH ₃ CH ₂ -G ₆ H ₄ E 20th 2- (CH ₃ ) ₂ CH-C ₆ H ₄ E 21st 3- (CH ₃ ) ₂ CH-C ₆ H ₄ Ę 22nd 4- (CH ₃ ) ₂ CH-C ₆ H ₄ Ę 23rd 2- (CH ₃ ) ₃ CC ₆ H ₄ Ę 24th 3- (CH ₃ ) ₃ CC ₆ H ₄ Ę 25th 4- (CH ₃ ) ₃ CC ₆ H ₄ Ę 26th 2-CH ₃ OC ₆ H ₄ E 27th 3-CH ₃ OC ₆ H ₄ E 28th 4-CH ₃ OC ₆ H ₄ E 29th 2-CF ₃ OC ₆ H ₄ Ę 30th 3-CF ₃ OC ₆ H ₄ Ę 31st 4-CF ₃ OC ₆ H ₄ Ę

table (continued)

The compound No. R Melting temp. (° C) olefinic * isomers * 32 2-C ₆ H ₅ OC ₆ H ₄ Ę 33 3-O-C6H ₅ C6H ₄ Ę 34 4-O-C6H ₅ C6H ₄ E 35 2-NO ₂ -C ₆ H ₄ Ę 36 3-NO ₂ -C ₆ H ₄ Ę 37 4-NO ₂ -CeH ₄ Ę 38 2-NH ₂ -C ₆ H ₄ Ę 39 3-NH ₂ -C ₆ H ₄ E 40 4-NH ₂ -C ₆ H ₄ Ę 41 2-C6H ₅ -C6H ₄ Ę 42 3-C ₆ H ₅ -C ₆ H ₄ E 43 4-C6H ₅ -C6H ₄ E 44 2-HO ₂ CC ₆ H ₄ Ę 45 3-HO ₂ CC ₆ H ₄ Ę 46th 4-HO ₂ CC ₆ H ₄ E 47 2-CH ₃ O ₂ CC ₆ H ₄ Ę 48 3-CH ₃ O ₂ CC ₆ H ₄ Ę 49 4-CH ₃ O ₂ CC ₆ H ₄ Ę

table (continued)

The compound No. R Melting temp. (° C) olefinic * isomers * 50 2- (CN) -C ₆ H ₄ E 51 3- (CN) -C ₆ H ₄ Ę 52 4- (CN) -C ₆ H ₄ Ę 53 2-HO-C ₆ H ₄ E 54 3-HO-C ₆ H ₄ E 55 4-HO-C ₆ H ₄ Ę 56 2-CH ₃ C (O) NH-C ₆ H ₄ Ę 57 3-CH ₃ C (O) NH-C ₆ H ₄ Ę 58 4-CH ₃ C (O) NH-C ₆ H ₄ Ę 59 2,3-di-FC ₆ H ₃ E 60 2,4-di-FC ₆ H ₃ E 61 2,5-di-FC ₆ H ₃ Ę 62 2,6-di-FC ₆ H ₃ E 63 3,4-di-F-C6H ₃ E 64 3,5-di-FC ₆ H ₃ E 65 2,3-di-Cr-C ₆ H ₃ E 66 2,4-di-Cl-C ₆ H ₃ Ę 67 2,5-di-Cl-C ₆ H ₃ Ę

table (continued)

The compound No. R Melting temp. (° C) olefinic * isomers * 68 2,6-di-Cl-C ₆ H ₃ E 69 3,4-di-Cl-C ₆ H ₃ E 70 3,5-di-Cl-C ₆ H ₃ E 71 2,3-di-CH ₃ -C ₆ H ₃ Ę 72 2,4-di-CH ₃ -C ₆ H ₃ Ę 73 2,5-di-CH ₃ -C ₆ H ₃ Ę 74 2,6-di-CH ₃ -C ₆ H ₃ Ę 75 3,4-di-CH ₃ -C ₆ H ₃ Ę 76 3,5-di-CH ₃ -C ₆ H ₃ Ę 77 2,3-di-CH ₃ OC ₆ H ₃ Ę 78 2,4-di-CH ₃ OC ₆ H ₃ Ę 79 2,5-di-CH ₃ OC ₆ H ₃ Ę 80 2,6-di-CH ₃ OC ₆ H ₃ E 81 3,4-di-CH ₃ O-C ₆ H ₃ Ę 82 3,5-di-CH ₃ OC ₆ H ₃ Ę 83 2-F, 3-CI-C ₆ H ₃ Ę 84 2-F, 4-CI-C ₆ H ₃ E 85 2-F, 5-CI-C ₆ H ₃ E

table (continued)

The compound No. R Melting temp. (° C) olefinic * isomers ^4- 86 2-F, 6-CI-C ₆ H ₃ E 87 3-F, 4-CI-C ₆ H ₃ E 88 3-F, 5-CI-C ₆ H ₃ E 89 2-CI, 3-FC ₆ H ₃ Ę 90 2-CI, 4-FC ₆ H ₃ E 91 2-CI, 5-FC ₆ H ₃ Ę 92 3-CI, 4-FC ₆ H ₃ E 93 2-F, 3-CH ₃ -C ₆ H ₃ E 94 2-F, 4-CH ₃ -C ₆ H ₃ Ę 95 2-F, 5-CH ₃ -C ₆ H ₃ Ę 96 2-F, 6-CH ₃ -C ₆ H ₃ E 97 3-F, 4-CH ₃ -C ₆ H ₃ Ę 98 3-F, 5-CH ₃ -C ₆ H ₃ E 99 2-CH _3j 3-FC ₆ H ₃ Ę 100 2-CH _3i 4-FC ₆ H ₃ E 101 2-CH _3i 5-FC ₆ H ₃ E 102 3-CH _3i 4-FC ₆ H ₃ Ę 103 2-F, 3-CH ₃ OC ₆ H ₃ E

table (continued)

The compound No. R Melting temp. (° C) olefinic * isomers * 104 2-F, 4-CH ₃ OC ₆ H ₃ Ę 105 2-F, 5-CH ₃ OC ₆ H ₃ Ę 106 2-F, 6-CH ₃ OC ₆ H ₃ E 107 3-F, 4-CH ₃ OC ₆ H ₃ Ę 108 3-F, 5-CH ₃ OC ₆ H ₃ Ę 109 2-CH ₃ O, 3-FC ₆ H ₃ Ę 110 2-CH ₃ O, 4-FC ₆ H ₃ E 111 2-CH ₃ O, 5-FC ₆ H ₃ Ę 112 3-CH ₃ O, 4-FC ₆ H ₃ E 113 2-Cl, 3-CH ₃ -C ₆ H ₃ E 114 2-Cl, 4-CH ₃ -C ₆ H ₃ E 115 2-Cl, 5-CH ₃ -C ₆ H ₃ Ę 116 2-Cl, 6-CH ₃ -C ₆ H ₃ E 117 3-Cl, 4-CH ₃ -C ₆ H ₃ Ę 118 3-Cl, 5-CH ₃ -C ₆ H ₃ E 119 2-CH ₃₎ 3-CI-C ₆ H ₃ Ę 120 2-CH _3j 4-CI-C ₆ H ₃ Ę 121 2-CH _3i 5 -Cl-C ₆ H ₃ Ę

table (continued)

The compound No. R Melting temp. (° C) olefinic * isomers * 122 3-CH ₃ , 4-CI-C ₆ H ₃ Ę 123 2-CI, 3-CH ₃ OC ₆ H ₃ Ę 124 2-CI, 4-CH ₃ OC ₆ H ₃ E 125 2 ~ CI, 5-CH ₃ OC ₆ H ₃ E 126 2-CI, 6-CH ₃ OC ₆ H ₃ E 127 3-CI, 4-CH ₃ OC ₆ H ₃ E 128 3-CI, 5-CH ₃ OC ₆ H ₃ E 129 2-CH ₃ O, 3-CI-C ₆ H ₃ Ę 130 2-CH ₃ O, 4-CI-C ₆ H ₃ Ę 131 2-CH ₃ O, 5-CI-C ₆ H ₃ Ę 132 3-CH ₃ O, 4-CI-C ₆ H ₃ E 133 2-CH _3i 3-CH ₃ OC ₆ H ₃ E 134 2-CH _3i 4-CH ₃ OC ₆ H ₃ Ę 135 2-CH ₃ , 5-CH ₃ OC ₆ H ₃ E 136 2-CH _3j 6-CH ₃ OC ₆ H ₃ E 137 3-CH _3i 4-CH ₃ OC ₆ H ₃ E 138 3-CH ₃ , 5-CH ₃ OC ₆ H ₃ E 139 2-CH ₃ O, 3-CH ₃ -C ₆ H ₃ Ę

table (continued)

The compound No. R Melting temp. (° C) olefinic * isomers * 140 '2-CH ₃ O, 4-CH ₃ -C ₆ H ₃ E 141 2-CH ₃ O, 5-CH ₃ -C ₆ H ₃ E 142 3-CH ₃ O, 4-CH ₃ -C ₆ H ₃ Ę 143 2,4,6-tri-F-C6H2 Ę 144 2,4,6-tri-Cl-C ₆ H ₂ E 145 2,4,6-tri-CH ₃ -C ₆ H ₂ E 146 2,6-di-F, 4-CI-C ₆ H ₂ E 147 2,6-di-Me, 4-FC ₆ H ₂ E 148 2,6-di-Cl, 4-FC ₆ H ₂ Ę 149 2,3,5,6-tetra-Cl-C ₆ H E 150 Pentafluorophenyl E 151 Pentachlorophenyl Ę 152 H E 153 ch ₃ E 154 ch ₃ ch ₂ E 155 ch ₃ ch ₂ ch ₂ Ę 156 (CH ₃ ) ₂ CH E 157 ch ₃ ch ₂ ch ₂ ch ₂ E

table (continued)

The compound No. R Melting temp. (° C) olefinic * isomers * 158 (CH ₃ ) ₃ C E 159 Cyclohexyl E 160 CH ₂ : CHCH ₂ Ę 161 EC ₆ H ₅ CH: CHCH ₂ Ę 162 CH ₂ : C (CH ₃ ) CH ₂ Ę 163 E-CH ₃ CH: CHCH ₂ E 164 2-tetrahydropyranyl E 165 2-pyridyl E 166 3-pyridyl E 167 4-pyridyl Ę 168 2- (5'-CF ₃ -pyridyl) E 169 2-pyrimidyl Ę 170 4-pyrimidyl E 171 5-pyrimidyl Ę 172 3,4-methylenedioxyphenyl Ę 173 1-Naphthyl Ę 174 2-naphthyl Ę

table (continued)

The compound No. R Melting temp. (° C) olefinic * isomers ⁺ 175 CH ₃ SCH ₂ E 176 C6H5SCH2 Ę 177 c ₆ H ₅ oil 6.24 Z 178 2-furyl Ę 179 3-furyl E 180 2-thiophenyl Ę 181 3-Thiophenyl Ę 182 2-pyrrolyl Ę 183 3-pyrrolyl Ę 184 C ₆ H ₅ CH ₂ Ę 185 C ₆ H ₅ CH (CH ₃ ) Ę 181 C ₆ H ₅ CH (CH ₃ ) ₂ Ę

+ Chemical shift of the singlet from the olefinic proton in the betamethoxyacrylate group (md from tetramethylsilane) Solvent: CDCI ₃ * Beta-methoxyacrylate group geometry.

table The table includes compounds of the general formula

wherein the group R includes all the groups listed in Table 4 for each of the substituents on the phenyl ring listed above. The acrylate group may in each case have either E- or Z- geometry.

Y Z 3-F H 4-F H 5-F H 6-F H 3-CI H 4-CI H 5-CI H 6-CI H 3-CH ₃ H 4-CH3 H 5-CH3 H 6-CH3 H 3-NO2 H

Y Z 4-NO2 H 5-NO2 H 6-NO2 H 5-CF3 H 3-NO2 5-CI 3-NO2 5-NO2 5-SCH3 H 4-CH3O 5-CH3O 4- (CH ₃ ) ₂ N H 4,5-methylenedioxy

table; SELECTED PROTONON NMR DATA Table shows selected proton NMR data for certain compounds described in Tables 1-5 and described there as oils. Chemical shifts are measured in mill. parts of tetramethylsilane, and deuteriochloroform was used everywhere as a solvent. The following abbreviations are used:

pi = wide s = singlet t = triplet q = quartet = doublet = m u pi pi et

Compound no. Table No. 3 1 1.27 (3H, t J7Hz), 3.83 (3H, s), 4.21 (2H, q J7Hz), 7.32 (5H, bs), 7.53 (1H, s). 4 1 1.30 (3H, t J7Hz), 3.72 (3H, s), 4.06 (2H, q J7Hz), 7.31 (5H, bs), 7.62 (1H, s). 5 1 1.27 and 1.31 (2 triplets J_7Hz, 3H each), 4.08 and 4.22 (2 quartets J 7Hz, 2H each), 7.33 (5H, pi s), 7.62 (1H, s). 6th 1 3.81 (3H, s), 5.21 (2H, s), 7.34 (10H, s), 7.56 (1H, s). 8th 1 1.49 (9H, s) 3.82 (3H, s), 7.31 (5H, pi s), 7.44 (1H, S) · 15th 1 1.42 (9H, s), 3.70 (3H, s), 6.50 (2H, s), 7.37 (1H, s). 16th 1 1.28 (9H, s), 3.83 (3H, s), 6.46 (2H, s), 7.87 (1H, s). 20th 1 3.67 (3H, s), 3.79 (3H, s), 5.18 (1H, dd J 11 and 1Hz), 5.65 (1H, dd J 18 and 1Hz), 6.68 (1H, dd J 18 and 1Hz) 11 Hz), 7.57 (1H, s). 26th 1 3.78 (3H, s), 3.95 (3H, s), 6.70 (1H, s). 28th 1 2.18 (3H, s), 3.68 (3H, s), 3.82 (3H, s), 7.55 (1H, s). 30th 1 3.68 (3H, s), 3.83 (6H, s), 7.25-7.6 (3H, m), 7.52 (1H, s), 7.9-8.1 (1H, m). 40 1 3.60 (3H, s), 3.66 (3H, s), 3.87 (2H, s), 7.48 (1H, s). 42 1 3.60 (3H, s), 3.70 (3H, s), 3.75 (3H, s), 3.80 (2H, s), 7.50 (1H, s).

Compound no. Table No. 45 1 3.6 (3H, s), 3.75 (3H, s), 7.0-8.15 (5H, m). 52 1 3.66 (2H, s), 3.76 (3H, s), 7.51 (1H, s). 53 1 3.56 (3H, s), 3.73 (3H, s), 7.1-7.7 (9H, m), 7.9-8.1 (1H, m). 57 1 3.73 (3H, s), 3.85 (3H, s), 7.54 (1H, s). 59 1 3.77 (3H, s), 3.91 (3H, s), 6.64 (1H, s). 65 1 3.05 (3H, s), 3.43 (3H, s), 3.61 (3H, s). 66 1 3.53 (3H, s), 3.67 (3H, s), 3.85 (3H, s), 7.32 (1H, s). 5 2 3.63 (3H, s), 3.78 (3H, s), 6.80-7.40 (8H, m), 7.46 d H, s). 6th 2 3.60 (3H, s), 3.76 (3H, s), 6.8-7.0 (4H, m), 7.14- 7.32 (4H, m), (1H, s). 7th 2 3.62 (3H, s), 3.77 (3H, s), 7.48 (1H, s). 28th 2 3.66 (3H, s), 3.80 (3H, s), 3.82 (3H, s), 6.8-7.3 (8H, m), 7.51 (1H, s). 66 2 3.65 (3H, s), 3.79 (3H, s), 7.48 (1H, s). 153 2 3.70 (3H, s), 3.79 (3H, s), 3.82 (3H, s), 7.53 (1H, s). 159 2 1.1-2.1 (10H, m), 3.65 (3H, s), 3.76 (3H, s), 4.20 (1H, pis), 7.38 (1H, s). 160 2 3.63 (3H, s), 3.80 (3H, s), 4.51 (2H, d), 5.05-6.39 (3H, m), 6.70-7.35 (4H, m), 7.46 (1H, s). 161 2 3.60 (3H, s), 3.74 (3H, s), 4.66 (2H, d), 6.00-7.40 (11H, m), 7.46 (1H, s).

Compound no. Table No. 181 2 3.54 (3H, s), 3.88 (3H, s), 6.60 (1H, s). 165 2 3.55 (3H, s), 3.74 (3H, s), 6.80 (1H, d), 6.95 (2H, m), 7.15-7.40 (4H, m), 7.43 (1H, s), 7.65 (1H, m), 8.19 (1H, m). 3 3 3.61 (3H, s), 3.78 (3H, s), 6.8-7.3 (8H, m), 7.47 (1H, s) · 5 3 3.69 (3H, s), 3.88 (3H, s), 6.84 (1H, d), 7.60 (1H, s), 8.10 (1H, dd), 8.20 (1H, d).

The compounds of formula (I) of the invention may be prepared from the substituted benzenes of formula (IV) according to the steps shown in Scheme I. In this scheme, R ¹ , R ² , X, Y and Z are as defined above, L is a halogen (iodine, bromine or chlorine) atom or hydrogen atom, and M is a metal atom (such as a lithium atom) or a metal atom with a bonded halogen atom (such as Mgl, MgBr or MgCl).

Thus, compounds of general formula (I) wherein R ¹ and R ² are non-hydrogen atoms can be obtained by treating ketoospheres of general formula (II: R ¹ non-hydrogen atom) with phosphoranes of general formula (V: R ² non-hydrogen atom) in a convenient solvent such as diethyl ether (see, for example, W Steglich, G. Schramm, T. Anke, and F. Obervvinkler, EP 0044448, July 4, 1980).

The ketoesters of general formula (II: R ¹ is not a hydrogen atom) can be obtained by treating metallized materials (III) with oxalate (VI, R ¹ is not a hydrogen atom) in a suitable solvent such as diethyl ether or tetrahydrofuran. More suitable methods often include the slow addition of a solution of metal materials (III) to a stirred solution of excess oxalate (VI) (see, e.g., LMV Westock, RBCurrie and AVLovell, Synthetic Communications, 1981, U.S. Pat. 943, and references therein).

Metallized materials (III) where M = Mgl, MgBr or MgCl (Grignard reagents) can be obtained by standard methods from the corresponding aromatic halides (IV) where L = 1, Br or Cl, respectively, with certain X, Y and Z substituents metallized materials (III) where M = Li can be obtained by direct lithiation of compounds of formula (IV) where L = H using a strong lithium base such as n-butyl lithium or lithium diisopropylamide (see, e.g. HWGschewend and HRRodriguez, Organic Reactions, 1979, 26.1).

Compounds of general formula (IV) may be obtained by standard methods described in the chemical literature.

Alternative methods for preparing ketoesters of the general formula (II: R ¹ are other than hydrogen) are described in the chemical literature (see, e.g., DCAtkinson, KEGodfrey, B. Meek, JFSaville, and MRStillings, J. Med. Chem., 1983, 26, 1353; D.Home, J.Gaudino and W.J.Thompson, Tetrahedron Lett. 25, 3529 (1984) and GPAxiotis, Tetrahedron Lett. 1981, 22, 1509).

Alternative methods for preparing the compounds of the general formula (I) of the present invention are illustrated in Scheme II below. In this scheme, R ¹ , R ² , X, Y and Z are as defined above.

The following are Scheme I and Scheme II above.

M

I Scheme co ₂ r ¹

y-H · (iv)

Scheme II

CH

A

1. hco ₂ r ¹

2. R ² Q

Compounds of the general formula (I) wherein R ¹ is not a hydrogen atom can be obtained by treating phenyl acetates of the general formula (VII: R ¹ is not a hydrogen atom) with a base and an ester such as methyl formate or HCO ₂ R ¹ where R ¹ is as defined above, but not a hydrogen atom, in a suitable solvent. If the reaction is quenched with a compound of general formula R ² Q wherein R ² is as defined above but not a hydrogen atom and Q is a leaving group such as a halogen atom, compounds of general formula (I) wherein R ² is not a hydrogen atom.

If, on the other hand, the reaction is quenched with water, compounds of formula (I) are obtained for which R ² = H.

Compounds of general formula (I) for which R ² = H can be converted into compounds of formula (I) for which R ² is not a hydrogen atom by successive treatment with a base (such as potassium carbonate or sodium hydride) and a substance of general formula R ² Q, wherein R ² and Q are as defined above in a suitable solvent.

In addition, compounds of general formula (I) wherein neither R ¹ nor R ² are hydrogen atoms can be obtained from acetals of general formula (VIII) for which neither R ¹ nor R ² is hydrogen or basic or acidic. conditions, suitable solvents and suitable temperatures. An example of a suitable base is lithium diisopropylamide and potassium hydrosulfate is an example of a suitable acidic reagent (see T. Yamada, H. Hagivvara and H. Oda, Journal of the Chem. Soc., Chem. Commun. 1980, 838, and therein). literary references).

Acetals of the general formula (VIII) for which neither R ¹ nor R ² are hydrogen atoms can be obtained from phenylacetate esters of the general formula (VII: R ¹ is not a hydrogen atom) by reacting the alkyl silyl ketene acetal derivatives of formula (VII) trialkyl orthoformates in the presence of Levvisic acid in a suitable solvent and at a suitable temperature (see, for example, K. Saigo, M. Osaki, and T. Mukaiyama, Chem. Letts. 1976, 769).

Alternative methods for preparing compounds of general formula (I) are shown in Scheme III. In this scheme, R ¹ , R ² , X, Y and Z are as defined above.

The following is Scheme III.

co ₂ r ¹

Thus, compounds of general formula (I) for which R ¹ is not a hydrogen atom and R ² = H can be obtained by partial reduction of the malonate derivatives (IX: R ¹ is not a hydrogen atom) using a reducing agent such as lithium aluminum hydride in a suitable solvent , such as diethyl ether (see, for example, Barczai-Beke, Dornyei, G.Toth, J.Tarnas and Cs. Szantay, Tetrahedron, 1976, 32,1153, and references therein).

In addition, compounds of general formula (I) may be prepared from acrylic acid derivatives of general formula (X) by reaction with bromine in a reagent of general formula R ² OM, wherein R ² and M are as defined above, and sodium hydrosulfate or a similar chemical (see, for example, G.Shaw and RNWarrener, Journal of the Chemical Society, 1958, 153, and references therein).

Compounds of general formulas (VII), (IX) and (X) may be prepared by standard methods described in the chemical literature.

All of the above methods, any part (step) or parts (steps) thereof, and their various combinations are considered to be part of the methods of the present invention.

The compounds and metal complexes of the present invention are active fungicides, especially against the following diseases:

Pyricularia oryzae rice, Puccinia recondita wheat, Puccinia striiformis and other rust, Puccinia hordei barley, Puccinia striiformis and other rust, rust of other plants such as coffee, pear, apple, peanut, vegetable and ornamental plant;

Barley, wheat Erysiphe graminis (powdery mildew), other powdery mildew in various crops such as Sphaerotheca macularis hops, Sphaerotheca fuliginea cucumber (e.g. cucumber Podosphaera leucotricha and Uncinula necator grape),

Cereal Helminthosporium species, Rhynchosporium species, Septoria species, Pseudocercosporella herpotrichoides and Gauomannomyces graminis;

Peanuts Cercospora arachidicola and Cercosporidium personata and other species of Cercospora in other crops such as sugar beet, banana, soybean and rice;

Botrytis cinerea (gray mold) in tomatoes, strawberries, vegetables, grapes and other crops;

Alternaria species in vegetables (for example, cucumbers), oilcress, apples, tomatoes and other plants;

Apples Venturia inaegualis (leprosy), Piasmopara viticola, other downy mildew such as lettuce Bremia lactucae, soybean, tobacco, onion and other plants of Peronospora, hops

Pseudoperonospora humuli and cucumber Pseudoperonospora cubensis, Phytophthora infestans and other species of Phytophthora in vegetables, strawberries, avocados, peppers, ornamental plants, tobacco, cocoa and other plants;

Thanatephorus cucumeris rice and other Phizoctonia species in other plants such as wheat and barley, vegetables, cotton and lawn grass.

Some compounds showed a broad spectrum of activity against fungi in vitro. They are active against various post-harvest diseases of the fruit (for example, orange Penicillium digitatum and italicum and Trichoderma viride, and banana Gloesporium musarum).

In addition, some compounds may be used for seed treatment against Fusarium species, Septoria species, Tilletia species (seed wheat stem), Ustilago species, Helminthosporium species in cereals, Phizoctonia solani in cotton and Pyricularia oryzae in rice.

The compounds can move acropetally in plant tissues. In addition, the compounds may be volatile enough to be active in the evaporation phase against fungi in plants.

The compounds may also be useful as industrial fungicides (as opposed to agricultural fungicides), for example, for protecting against fungus on wood, hides, skin and especially dyed films.

Some compounds show herbicidal activity and can be used at higher rates to control weeds.

Similarly, some compounds show plant growth regulatory activity and can be used for this purpose, again under suitable conditions.

Therefore, the present invention encompasses the use of the above compounds (compositions containing these compounds) as a supplement to their basic use as fungicides.

The individual compounds themselves can be used for fungicidal purposes, but it is more convenient to formulate compositions for such use. Thus, the present invention provides a fungicidal composition comprising a compound of general formula (I) as hereinbefore defined, or a metal complex thereof, and optionally a carrier or diluent.

The invention also provides a method for controlling fungi, which comprises applying the compound or a metal complex thereof to a plant, a plant seed or a plant or garden plant site.

The compounds and metal complexes of the present invention can be used in a variety of ways. For example, they can be used in compositions or individually as such, directly in the treatment of plants, i.e. plant leaves, or they can also be used for shrubs and trees, seeds and the environment in which plants, shrubs or trees grow or need to be planted, or they can be sprayed, sprayed or applied as a cream or paste, or used as steam , or as slow release granules. Can be used on any part of a plant, shrub or tree, such as leaves, stems, branches or roots, or soil surrounding roots or seeds before planting; or in general for soil, irrigation water, or hydroponic cultivation systems. The compounds of the invention may be injected into plants or trees or sprayed on vegetation using electrodynamic spraying techniques or other low volume methods.

As used herein, the term "plant" includes sprouts, shrubs and trees. In addition, the fungicidal method of the invention comprises the treatment of a prophylactic, protective and antifungal agent.

The use of the compounds in the form of compositions for agricultural and horticultural purposes is preferred. The type of composition used in each case will depend on the particular purpose.

The compositions may be in the form of a dusting powder or granules, consisting of the active ingredient and a solid solvent or carrier, for example, fillers such as kaolin, bentonite, infuser earth, dolomite, calcium carbonate, talc, magnesium powder (magnesium oxide), gypsum, Hewitt earth, diatomite, and Chinese clay. Such pellets can be pre-made suitable for use in the soil without further treatment. These granules can be made either by impregnating the filler beads with the active ingredient, or by granulating a mixture of the active ingredient and powdered filler. Seed dressing compositions may, for example, include a substance (e.g., mineral oil) that improves seed adhesion; alternatively, the active ingredient for seed dressing may be incorporated using an organic solvent (e.g., N-methylpyrrolidone or dimethylformamide).

The compositions may also be in the form of dispersible powders, granules or pellets containing a wetting agent to facilitate dispersion of the powders or pellets in liquids, which may also contain excipients and suspensions.

Aqueous dispersions or emulsions may be prepared by dissolving the active ingredient (s) in an organic solvent, possibly containing a wetting, dispersing or emulsifying agent (s), and then adding the mixture to water containing the wetting, dispersing or emulsifying agent (s). Suitable organic solvents include ethylene dichloride, isopropylene alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, xylenes, trichlorethylene, furfuryl alcohol, tetrahydrofurfuryl alcohol, and glycol ethers (e.g., 2-ethoxyethanol and 2-butoxy).

Formulations for nebulization may also be in the form of aerosols, wherein the mixture is contained in a pressurized container in the presence of a propellant such as fluorotrichloromethane or dichlorodifluoromethane.

The compounds may be mixed dry with the pyrotechnic composition to form compositions to generate smoke in confined spaces containing these compounds.

Alternatively, the compounds may be used in the form of microcapsules. They can also be incorporated into biodegradable polymeric devices, also resulting in slow, controlled release of the active ingredient.

By incorporating suitable additives, such as additives for improving partitioning, adhesion strength, rain resistance on the surfaces to be treated, different compositions can be better adapted for different purposes.

These compounds can be used as mixtures with fertilizers (e.g. nitrogen, potassium or phosphorus-containing fertilizers). Preference is given to compositions which consist exclusively of fertilizer granules which activate the active compound, for example, coated with it. Such granules generally contain up to 25% by weight of this compound. The invention thus also provides a fertilizer composition comprising a compound of the general formula (I) or a metal complex thereof.

The compositions may also be in the form of liquid preparations for application by dipping or spraying, which are generally aqueous dispersions or emulsions containing the active ingredient in the presence of one or more surfactants, for example, wetting, dispersing, emulsifying, ) or suspending agent (s): or they are a means of application suitable for electrodynamic application. The above materials may be cationic, anionic or nonionic. Suitable cationic materials are quaternary ammonium jets such as cetyltrimethylammonium bromide.

Suitable anionic materials include soaps, salts of aliphatic monoesters of sulfuric acid (e.g., sodium lauryl sulfate) and salts of sulfonated aromatic compounds (e.g., sodium dodecylbenzenesulfonate, sodium, potassium or ammonium lignosulfonate, butylnaphthalene sulfonate and sodium diisopropyl) and diisopropyl sodium.

Suitable condensation products of a nonionic material ethylene oxide with fatty alcohols such as oleyl or cetyl alcohol or alkyl phenols such as octyl or nonyl phenol and octylcresol. Other nonionic materials include partial esters derived from long chain fatty acids and hexitol anhydrides, ethylene oxide condensation products of said partial esters, and lecithins. Suitable suspending agents are hydrophilic colloids (e.g., polyvinylpyrrolidone and sodium carboxymethylcellulose) and plant resins (e.g., acacia or tragacanth).

Compositions for use as aqueous dispersions or emulsions are generally supplied as a concentrate containing a significant proportion of the active ingredient (s), and the concentrate is diluted with water prior to use. Such concentrates must withstand storage for a prolonged period of time, after which they must remain water soluble to obtain aqueous formulations which remain homogeneous for a sufficient period of time using conventional and electrodynamic spraying equipment. Concentrates generally contain up to 95%, preferably 10-85%, for example 25-60%, of the active ingredient (s). These concentrates usually contain organic acids (for example, alkaryl or aryl sulfuric acids such as xylene sulfuric acid or dodecyl benzene sulfuric acid), since the presence of such acids increases the solubility of the active ingredient (s) in polar solvents commonly used in concentrates. The concentrates usually contain a large proportion of the surfactants to obtain sufficiently stable emulsions in water. After reconstitution with aqueous preparations, such formulations may contain various amounts of the active component (s), depending on the intended use, but may include aqueous formulations containing from 0.0005 or 0.01 to 10% by weight of the active ingredient (s). .

The compounds of the present invention may also contain other compound (s) having biological activity, for example compounds having similar or additional fungicidal activity, or compounds having plant regulatory, herbicidal or insecticidal activity.

Another fungicidal compound may be, for example, a compound capable of combating cereal (e.g. wheat) bean diseases such as Septoria, Gibberella and Helminthos porium species, seed and soil-borne diseases, fake and true grapevine, apple pox and the like. These fungicidal compounds may have a broader spectrum of activity than the compound of general formula (I) alone; in addition, another fungicide may have a synergistic effect on the fungicidal activity of the compound of general formula (I). Examples of other fungicidal compounds include carbendazim, benomyl, thiophanate-methyl, thiabendazole, fuberidazole, etridazole, dichlofluanid, cymoxanyl, oxadixyl, opurazole, metalaxyl, furalaxyl, beniaxyl, fosetylaluminum, fenarimol, iprodol, S3308, pyrazophos, etirimol, ditalymphos, triforin, nuarimol, triazbutyl, guazatin, propiconazole, prochloraz, flutriafol, chlortriafol, ie substance 1- (1,2,4-triazol-1-yl) -2- (2,4-dichlorophenyl) -hexan-2-ol, DPX H6573 (1- (bis-4-fluorophenyl) methylsilyl) methyl) 1H- 1,2,4-triazole, triadimefon, triadimenoia, diclobutrazole, fenpropimorph, fenpropidin, triademorph, imazalil, fenfuram, carboxin, oxycarboxin, metfuroxam, dodemorph, BAS 454, blasticidine S, Kasugamycin, edifenphos, isazin, , tricyclazole, pyroquilane, chlorobenzthiazone, neoazosin, polyoxin D, validamycin A, repronil, phytolanias, pencicuron, diclomezine, phenazine oxide, nickel dimethyldithiocarbamate, techlorphthalam, bitertanol, bupirimate, chitofurazole, chitofuram, ethanazole, streptomol, -methyl, piroxifur, polyram, maneb, mansozeb, captafol, chlorothalonil, anilazine, thiram, captan, folpet, zineb, propineb, sulfur, dinocap, binapacryl, nitrotal-isopropyl, dodine, dithianone, f entine hydroxide, fentin acetate, techazene, quintozene, dichlorane, copper-containing compounds such as copper oxychloride, copper sulfate and Bordeaux blend, and organo-copper compounds such as 1- (2-cyano-2-methoxyiminoacetyl) -2-ethylurea.

The compounds of the general formula (I) may be admixed with soil, peat or other media for rooting of plants to protect against fungal diseases which may be caused by seeds, soil or leaves.

Suitable insecticides include pirimicarb, dimethoate, demeton-s-methyl, formation, carbaryl, isoprocarb, XMC, BPMC, carbofuran, carbosulfan, diazinon, fenthion, fenitrothion, pheneno, chlorpyrifos, isoxathion, propafos, monocrotophene, buprofez, buprofez.

A plant growth regulator may be a compound that regulates the growth of weeds or the formation of a seed head, or selectively controls the growth of less desirable plants (e.g. grasses).

Suitable examples of plant growth regulating compounds for use with the compounds of the invention include gibberellins (e.g., GA ₃ , GA ₄ or GA ₇ ), auxins (e.g., indolacetic acid, indole-butyric acid, naphthoxyacetic acid or naphthylacetic acid), cytokinins (e.g., kinetin, diphenylurea, benzimidazole, benzyladenine or benzylaminopurine), phenoxyacetic acids (e.g. 2,4-D or MCPA), substituted benzoic acids (e.g. triiodobenzoic acid), morphactines (e.g. chlorofluorecol), maleic hydrazide, glyphosate, glyphosine, long chain fatty alcohols and acids, dicegulac, paclobutrazole, flurprimidol, fluoride amide, mefluidide, substituted quaternary ammonium and phosphonium compounds (such as chlormequat, chlorphonium or mepiquat chloride), ephephon, carbetamide, methyl-3,6-dichloroanisate, daminozide, asulam,

1- (4-chlorophenyl) -4,6-dimethyl-2-oxo-1,2-dihydropyridine-3-carboxylic acid, hydroxybenzonitriles (e.g. bromoxynil), difenzoquate, benzoylprop-ethyl 3,6-dichloropicolinic acid, paclobutrazole, fenpentezole , inabenfide, triapentenol, and techazene.

The following examples illustrate the invention. In these examples, the term "ether" refers to diethyl ether, magnesium sulfate is used to dry solutions, and reactions involving water-sensitive intermediates were carried out under a nitrogen atmosphere. Unless otherwise stated, chromatography was performed using silica gel as the stationary phase. Where shown, IR and NMR data are retrieved; no attempt was made to indicate each absorbance. The following abbreviations are used:

THF = tetrahydrofuran

DMF = N, N-dimethylformamide

DC = gas chromatography MS = mass spectrum s = singlet d = doublet t = triplet m = multiplet

EXAMPLE 1

This example illustrates the preparation of 2E, T'Z-methyl 3-methoxy-2- [2 '- (2' -phenylethenyl) phenyl] propenoate (compound 13 in Table 1).

Potassium tert-butoxide (5.30 g) was added (all at once) to a vigorously stirred suspension of benzyltriphenylphosphonium chloride (21.02 g) in dry ether (250 mL). After 25 minutes, the resulting orange mixture was treated with a solution of 2-bromobenzaldehyde (5.00 g) in dry (50 mL) ether and the mixture lightened. After another hour, the mixture was poured into water and extracted with ether. The extracts were washed with water, dried, concentrated under reduced pressure and chromatographed using dichloromethane as eluent to give 1-phenyl-2- (2-bromophenyl) ethylene (5.95 g, 85% yield) as an almost colorless oil as 6: 1. Z: Mixture of E-isomers (by DC / MS).

A solution of a portion of the isomer mixture of Grignard's reagent from 1-phenyl-2- (2-bromophenyl) -ethylene described above (5.58 g) and magnesium (0.63 g) in dry THF (20 mL) was added dropwise over 30 minutes. to a stirred solution of dimethyl oxalate (5.06 g) in dry THF (40 mL) cooled to -15 ° C. The resulting mixture was stirred at about -15 ° C for 30 minutes, then at room temperature for 1 hour, then was added to dilute hydrochloric acid and extracted with ether. The extracts were washed with water, dried, concentrated under reduced pressure, then chromatographed twice [(i) 30% ether in gasoline, (ii) 20% hexane in dichloromethane] to give the isomerically pure Z-methyl 2- (2'-phenylethenyl) phenylglyoxalate. (1,76g, 31% yield) as a yellow oil, ¹ H NMR (CDCl _3): delta 3.87 (3H, s), 6.78 (doublet 2-center, each 1H, J = 12 Hz) ppm

Potassium tert-butoxide (2.00 g) was added (all at once) to a stirred suspension of (methoxymethyl) -triphenylphosphonium chloride (6.78 g) in dry ether (80 mL). After 25 minutes, the resulting red suspension was treated with a solution of Zmethyl 2- (2'-phenylethenyl) -phenylglyoxalate (1.76 g) in dry ether (20 mL) and the color lightened. After 1.5 hours, the reaction mixture was poured into water and extracted with ether. The extracts were washed with water, dried, passed through a short silica gel column with dichloromethane, then carefully chromatographed using 30% ether in petrol as eluent to afford the title compound (0.46 g, 24% yield) as an oil, IR (strip): 1715, 1635 cm ^-1 , ¹ H NMR (CDCl ₃ ): delta 3.62 (3H, s), 3.73 (3H, s), 6.48 (2H, s), 7.50 (1H, s) ) md

EXAMPLE

This example illustrates the preparation of E, and Z-methyl 3-methoxy-2-phenylpropenoate (compounds 1 and 2 in Table 1).

Potassium tert-butoxide (9.52 g) was added (all at once) to a stirred suspension of (methoxymethyl) -triphenylphosphonium chloride (34.3 g) in dry ether (300 mL). After 45 minutes, the resulting red suspension was treated with a solution of benzoyl formate (8.20 g) in dry ether (100 mL) (color lightening; exothermic reaction). After 3 hours, the mixture was diluted with water, treated with magnesium sulfate and charcoal, then concentrated under reduced pressure to give the crude (36.39 g) as a yellow oil which partially crystallized on standing. It was passed through silica gel using dichloromethane then carefully chromatographed using dichloromethane: gasoline (2: 1) to give E-methyl 3-methoxy-2-phenylpropenoate (4.83 g, 50% yield) as a pale yellow oil, which eluted first (elution), IR (band): 1715, 1630 cm ^-1 , ¹ H NMR (CDCl ₃ ): delta 7.55 (s, olefinic proton) and Z62 methyl 3-methoxy-2-phenylpropenoate (3, 43 g, 36% yield) as a pale yellow oil which eluted (elution) second, IR (band): 1715, 1630 cm ^-1 , ¹ H NMR (CDCl ₃ ): delta 3.76 (3H, s), 3 , 90 (3H, s), 6.65 (1H, s), 7.28 (5H, s) md

E-methyl 3-methoxy-2-phenylpropenoate obtained from methyl phenylacetate by the methods described in Examples 4 and 7, m.p. reaction with sodium hydride and methyl formate and treatment of the obtained enol with potassium carbonate and dimethyl sulphate, the sample solidified on standing and melted. temperature 37-38 ° C.

EXAMPLE

This example illustrates the preparation of 2E, 1Έ-, and 2Z, ΤΈ-methyl 3-methoxy-2- [2 '- (2 ”phenylethenyl) phenyl] propenoate (compounds 9 and 10 in Table 1).

A solution of 2-bromobenzaldehyde (18.50 g) in dry ether (20 ml) was added dropwise to a stirred solution of benzyl magnesium chloride [prepared from benzyl chloride (12.64 g) and magnesium (2.68 g)] in dry ether (120 ml), and drip formed a thick precipitate. The mixture was stirred for one hour at room temperature, then added to water acidified with 2M hydrochloric acid and extracted with ether. The extracts were washed with water, dried, concentrated and chromatographed using dichloromethane and gasoline (1: 1) as eluent to give 1- (2-bromophenyl) -2-phenylethan-1-ol (10.95 g, 40%), as a white solid, m.p. temp. 84-85 ° C.

A stirred mixture of 1- (2-bromophenyl) -2-phenyl-ethan-1-ol (15.50 g) and orthophosphoric acid (150 mL) was heated at 170 ° C for one hour, then poured into iced water and extracted with ether. . The extracts were washed with water, dried and concentrated to give the crude product as an orange oil (14.29 g).

Evaporation (0.3 torr pressure; bath temperature 140 ° C) gave E-1-phenyl-2- (2-bromo-phenyl) ethylene (12.53 g, 86% yield) as a pale yellow oil of purity 97 % DC.

A solution of Grignard's reagent from E-1-phenyl-2- (2-bromophenyl) ethylene (8.56 g) and magnesium (0.96 g) in dry tetrahydrofuran (20 mL) was added dropwise to stirred dimethyl oxalate over 30 minutes. (7.76 g) in dry tetrahydrofuran (70 mL) cooled to about -15 ° C. The resulting mixture was stirred at this temperature for 30 minutes, then at room temperature for one hour, then added to dilute hydrochloric acid and extracted with ether. The extracts were washed with water, dried, concentrated to give the crude product as a yellow oil (17.22 g). Purification by column chromatography using dichloromethane / petrol (1: 1) as eluent followed by evaporation (0.07 torr, bath temperature 170 ° C) gave E-methyl 2- (2'-phenylethenylyl) phenylglyoxalate (2.01 g). , 23% yield) as yellow oil, pure by DC, ¹ H NMR (CDCl 3): delta 3.78 (3H, s), 6.88 (2 doublet center, each 1 H, J 16 Hz) md

Potassium tert-butoxide (2.19 g) was added (all at once) to a stirred suspension of (methoxymethyl) -triphenylphosphonium chloride (7.41 g) in dry ether (100 mL). After 25 minutes, the resulting red suspension was treated with a solution of E-methyl-2- (2'-phenylethenyl) -phenylglyoxalate (1.92 g) in dry ether (20 mL) and the color lightened. After 15 minutes, the mixture was poured into water and extracted with ether. The extracts were washed with water, dried and chromatographed using 30% ether in gasoline as eluent to afford (i) 2E, the T'EJzomer of the title which was eluted (elution) first as a pale yellow oil (1.06 g, 50% yield) which crystallized on standing to give a white solid, m.p. temp. 103-104 ° C. The analytical sample, crystallized from an ether-gasoline mixture, had a melting point of 107-108 ° C. temp., IR (nujole): 1700, 1630 cm ^-1 , ¹ H NMR (CDCl 3): delta 3.68 (3H, s), 3.80 (3H, s), 7.06 (2H, s), 7.63 (1H, s) md; and (ii) the 2Z, 1 ′ E-isomer of the title which was eluted second as a viscous oil (0.260 g, 12% yield), IR (strip) 1710, 1625 cm ^-1 ; ¹ H NMR (CDCl ₃ ): delta 3.65 (3H, s), 3.92 (3H, s), 6.57 (1H, s), 6.99 and

7.24 (1H each, D J_16Hz) m.d.

EXAMPLE

This example illustrates the preparation of E-methyl 2- (2-chloro-6-fluorophenyl) -3-methoxypropenoate (Compound 27 in Table 1).

A mixture of methyl (2-chloro-6-fluorophenyl) acetate (5.20 g) and methyl formate (31.4 mL) in dry DMF (40 mL) was added dropwise to a stirred suspension of sodium hydride (1.23 g) in dry DMF (40 mL). ml) at a temperature between 0 and 5 ° C. Intense gas evolution was observed. The reaction mixture was stirred at room temperature for 3.5 hours, then poured into an ice / aqueous sodium carbonate mixture and washed with ether. The resulting aqueous mixture was acidified with concentrated hydrochloric acid and extracted with ether. The extracts were washed with water, dried and concentrated to give methyl 2- (2-chloro-6-fluorophenyl) -3-hydroxypropenoate (3.44 g) as a white solid.

A stirred solution of this crude product in dry DMF (30 mL) was treated successively with potassium carbonate (4.11 g) and dimethyl sulfate (1.34 mL). The resulting mixture was stirred at room temperature for 1 hour, then poured into water and extracted with ether. The extracts were washed with water, dried and concentrated to give the title compound (2.91

(g) as a white hardwood, melt. temp. 77-78 ° C. Colorless crystals [2.61 g, 42% yield of methyl (2-chloro-6-fluorophenyl) acetate], m.p. temp. 79-80 ° C, ¹ H NMR (CDCl ₃ ): delta 3.69 (3H, s), 3.84 (3H, s), 7.62 (1H, s), md

EXAMPLE

This example illustrates the preparation of E-methyl 2- (2-phenoxy) phenyl-3-methoxyacrylate (compound 1 in Table 2).

Potassium tert-butoxide (5.6 g) was added to a stirred solution of diphenyl ether (12.3 g) in dry ether (150 mL) at -70 ° C. The resulting mixture was stirred at this temperature for 15 minutes, then n-butyl lithium (30.5 mL of a 1.62 M solution in hexane) was added to give a red-brown suspension which was allowed to warm to room temperature. This mixture was added to a stirred suspension of dimethyl oxalate (11.8 g) in ether (250 mL) at -10 ° C for 20 minutes, then allowed to warm to room temperature. After 30 minutes, it was poured into water and extracted with ether. The combined extracts were washed with water, dried, then concentrated to give a red oil (14.21 g). Chromatography on 20% ether in petrol as eluent gave methyl 2-phenoxybenzoylformate (2.23 g) as a yellow oil.

Potassium tert-butoxide (2.64 g) was added to a vigorously stirred suspension of (methoxymethyl) triphenylphosphonium chloride (8.93 g) in dry ether (100 mL). After 20 minutes, the resulting red suspension was treated with a solution of methyl 2-phenoxybenzoylformate (2.23 g) in dry ether (20 mL) and the color lightened. After 15 minutes, the mixture was poured into water and extracted with ether. The combined extracts were washed with water, dried and concentrated to give a yellow oil (7.30 g). Chromatography on dichloromethane as eluent gave the title compound (0.61 g) as a colorless oil, IR (band): 1710, 1635 cm @ ^-1 ; ¹ H NMR: delta 3.60 (3H, s), 3.75 (3H, s), 7.47 (1H, s) md

EXAMPLE

This example describes an alternative method for preparing E-methyl 2- (2-phenoxy) phenyl-3-methoxypropenoate (compound 1 in Table 2).

A 1M solution of borane-tetrahydrofuran complex (30 mL) was added dropwise to a stirred solution of 2-phenoxybenzoic acid (5.35 g) in dry THF (50 mL) cooled to 0 ° C (vigorous evolution of gas). After instillation, the mixture was stirred at 0 ° C for 15 minutes, then at room temperature for 1.5 hours. The mixture was then poured into water and extracted with ether. The extracts were washed successively with water, aqueous sodium bicarbonate, aqueous sodium carbonate, then dried and concentrated under reduced pressure to give 2-phenoxybenzyl alcohol (4.83 g, 97%) as a colorless oil. To a solution of 2-phenoxybenzyl alcohol (4.80 g) in dry dichloromethane (50 mL) was added thionyl chloride (1.92 mL) (all at once). The resulting mixture was stirred at room temperature for 2 hours then washed with water (x2), aqueous sodium bicarbonate (x2), and aqueous sodium chloride, dried and concentrated under reduced pressure to give 2-phenoxybenzyl chloride (4.87 g, 93%) as a colorless oil.

Carbon dioxide was added to a solution of 2-phenoxybenzylmagnesium chloride [from 2-phenoxybenzyl chloride (4.80 g) and magnesium turnings (0.64 g)] in dry ether (15 mL) cooled to 0 ° C. Dry THF was added to increase solubility. When the exothermic reaction was complete, carbon dioxide was no longer allowed to pass through the mixture, which was allowed to warm to room temperature. The mixture was poured into water, washed with ether, then treated with hydrochloric acid and extracted with ether. The extracts were washed with water, dried and concentrated under reduced pressure to give 2-phenoxyphenylacetic acid (3.06 g, 61%) as a solid, m.p. temp. 82-85 ° C. Analytical sample crystallized from ether / gasoline m.p. temp. was 85-86 ° C.

A solution of 2-phenoxyacetic acid (2.75 g) in dry methanol (30 mL) containing sulfuric acid (0.3 mL) was heated under reflux for 2 hours, then allowed to cool, then the solution was poured into water and extracted ether. The extracts were washed with water, dried and concentrated under reduced pressure to give methyl 2-phenoxyphenyl acetate (2.65 g, 91%) as a pale yellow oil.

This ester was converted to the title compound via Step 2 using the procedure described in Example 4, m.p. reaction with sodium hydride and methyl formate and treatment of the resulting enol with potassium carbonate and dimethyl sulfate (total yield = 65%).

EXAMPLE

This example illustrates the preparation of E-methyl 2- (2-benzyloxy) phenyl-3-methoxyacrylate (Compound 177 in Table 2).

A mixture of methyl formate (24.4 mL) and methyl o- (benzyloxy) phenylacetate (5.10 g) in dry DMF (30 mL) was added dropwise to a stirred suspension of sodium hydride (0.95 g) in dry DMF (30 mL). At 5 ° C. Excessive gas evolution was observed. The reaction mixture was stirred at room temperature for 3.5 hours, then poured into a mixture of ice and aqueous sodium carbonate. The aqueous solution of guat was washed with ether (x3), then acidified with concentrated hydrochloric acid and extracted with ether. The extracts were washed with water, dried and concentrated to give methyl 2- (2-benzyloxy) phenyl-3-hydroxyacrylate (4.38 g) as a yellow oil.

Potassium carbonate (4.26 g) and dimethyl sulfate (1.38 mL) were sequentially added to a stirred solution of methyl 2- (2-benzyloxy) phenyl-3-hydroxyacrylate (4.38 g) in dry DMF (40 mL). After one hour at room temperature, the reaction mixture was poured into water, extracted with ether, dried, concentrated and triturated with gasoline to give the title compound (3.38 g, 57% yield as methyl o- (benzyloxy) phenylacetate) as a white solid, m.p. . temp. 74-75 ° C. After crystallization of the whole sample, colorless crystals (2.35 g) were obtained from methanol, m.p. temp. 76-77 ° C ¹ H NMR (CDCl): delta 3.63 (3H, s), 3.76 (3H, s), 5.05 (2H, s), 7.49 (1 H, s) md

EXAMPLE

This example describes the preparation of E-methyl 2- (4-chlorophenyl) -3-methoxypropenoate (compound 22 in Table 1).

A solution of methyl 4-chlorophenyl acetate (3.51 g) in dry THF (25 mL) was added dropwise to a stirred mixture of lithium diisopropylamide [diisopropylamine (2.88 g) and n-butyl lithium (16.4 mL of 1.62M). n-hexane)] solution in dry TMF (25 mL) at -70 ° C. After 0.5 h at the same temperature, a solution of trimethylsilyl chloride (5.16 g) in dry TMF (5 mL) was added and after 10 min the solution was allowed to warm to room temperature. The volatile components of the resulting mixture were removed under reduced pressure, and the soluble fraction remaining in ether was triturated with dry ether, filtered, and the filtrate concentrated under reduced pressure. This gave crude methylsilyl enol ether (5.18 g) as an orange oil with almost no carbonyl absorption IR spectrum with a peak at 1640 cm ^-1 .

A solution of titanium tetrachloride (3.60 g) in dry dichloromethane (5 mL) was added dropwise to a stirred solution of trimethylorthoformate (1.92 g) in dry dichloromethane (30 µl) at -70 ° C. After 15 minutes at the same temperature, a solution of crude methylsilyl enol ether described above (5.18 g) in dry dichloromethane (20 mL) was added at -70 ° C. After 0.5 h, aqueous potassium carbonate was added to the reaction mixture at -70 ° C, and it was extracted with ether. The extracts were washed with water, dried, concentrated under reduced pressure and chromatographed using ether: petrol (1: 1) as eluent to give methyl 2- (4-chlorophenyl) -3,3-dimethoxypropanoate (2.26 g, 46% yield). methyl 4-chlorophenyl acetate) as a solid, m.p. temp. 61-62 ° C.

A solution of methyl 2- (4-chlorophenyl) -3,3-dimethoxypropanoate (1.65 g) in dry THF (20 mL) was added dropwise at -70 ° C to a stirred lithium diisopropylamide [from diisopropylamine (0.84 g) and n-butyl lithium (4.7 mL of a 1.62M solution in n-hexane)] in dry THF (20 mL). After half an hour at 70 ° C, the reaction mixture was poured into water and extracted with ether. The extracts were washed with water, dried, concentrated under reduced pressure and chromatographed using 40% ether in petrol as eluent to give the title compound (0.31 g, 21%) as a pale yellow solid, m.p. temp. 61-62 ° C, IR (nujole) 1685, 1615 cm ^-1 , ¹ H NMR (CDCl ₃ ): delta 3.74 and 3.88 (each 3H, s), 7.56 (1H, s) md

EXAMPLE

This example describes the preparation of E-methyl 2- [2- (4-methylphenoxy)] - phenyl-3-methoxypropenoate (compound 16 in Table 2).

4-Methylphenol (8.40 g) was added to a stirred methanolic solution of sodium methoxide [from sodium (1.78 g) and dry methanol (50 mL)]. After 0.5 h, methanol was removed under reduced pressure and the residue was mixed with 4-methylphenol (4.20 g), 2-chloroacetophenone (6.00 g) and catalytic copper bronze. The resulting mixture was heated at 135 ° C for 1.5 hours, then allowed to cool, diluted with water and extracted with ether. The extracts were washed successively with aqueous sodium hydroxide and aqueous sodium chloride, then dried and concentrated under reduced pressure to give a dark oil (8.20 g). This crude product was purified by evaporation distillation (130-135 ° C at 0.02 tor) to give 2- (4-methyl-phenoxy) -acetophenone (7.29 g, 83%) as a colorless liquid, IR (strip) 1670 cm ' ¹ .

A solution of boron trifluoride etherate (18.06 g) and 2- (4-methylphenoxy) -acetophenone (7.29 g) in dry methanol (8.3 mL) was added to a stirred ice-cooled suspension of lead tetraacetate (14.97 g) in dry ether (70 mL). The resulting mixture was stirred at room temperature for 18 hours, then poured into water and extracted with ether. The extracts were washed successively with water and aqueous sodium bicarbonate, dried and concentrated under reduced pressure to give a red oil (7.53 g) containing methyl 2- (4-methylphenoxy) phenylacetate and starting acetophenone (4: 1 by DC). The mixture was treated with aqueous potassium hydroxide and the resulting substituted phenylacetic acid was purified by acid-base extraction and re-esterified in acidic methanol to give 2- (4-methylphenoxy) phenylacetate (5.00 g) as a thick oil, IR (strip): 1730 cm @ ^-1 .

This ester was converted to the title compound in a two-step manner as described in Examples 4 and 7, namely reaction with sodium hydride and methyl formate and treatment of the resulting enol with potassium carbonate and dimethyl sulfate (total yield = 32%). After recrystallization from methanol, the product melts. temp. 80-81 ° C IR (Nujol): 1690, 1620 ^{cm-1, 1H} NMR (CDCl): delta 2.30 (3H, s), 3.77 (3H, s), 7.50 (1 H , s) md

EXAMPLE

This example describes the preparation of E and Z-methyl 3-methoxy-2- (2-phenylethyl) propenoate (compounds 1 and 177 in Table 4).

Trifluoroacetic acid (46 mL) was added to a stirred mixture of 1- (2-bromophenyl) -2-phenylethan-1-ol (16.51 g obtained as described in Example 3) and triethylsilane (13.80 g) all at once. . The resulting mixture was stirred at room temperature for 22 hours, then trifluoroacetic acid was removed under reduced pressure. The residue was dissolved in ether and washed successively with water, aqueous sodium bicarbonate (x3) and water, then dried, concentrated under reduced pressure and chromatographed using 10% dichloromethane in gasoline as eluent to give 1- (2-bromophenyl) -2-phenylethan ( 8.02 g, 52%) as a colorless oil.

This sample of 1- (2-bromophenyl) -2-phenylethane was converted to the title compound in a two-step manner as described in Examples 1 and 3, namely the reaction of a magnesium derivative with dimethyloxalate and treatment of the resulting ketoester with methoxymethylene phenyl phosphorane. The E-isomethane eluted (elution) first in 30% ether in gasoline was oil, IR (band): 1705 and 1630 cm ^-1 , ¹ H NMR (CDCl 3): delta 2.79 (4H, s), 3.69 ( 3H, s), 3.79 (3H, s), 7.59 (1H, s) md

The Z-isomer washed second was also an oil, IR (band): 1715, 1695 and 1630 cm ^-1 , ¹ H NMR (CDCl 3): delta 2.84 (4H, s), 3.68 (3H, s) ), 3.84 (3H, s), 6.24 (1H, s) md

EXAMPLE

This example illustrates the preparation of 2E, ΤΈ-, and 2Z, 1'-E-methyl 2- [2 '- (2' - [2 '' - furyl] ethenyl) phenyl] -3-methoxypropenoate (compounds 55 and 56 in Table 1).

A mixture of 2-bromobenzyl bromide (12.10 g) and trimethyl phosphite (8.56 mL) was stirred in a flask fitted with a condenser on a redistillation head. This reaction mixture was heated at 110 ° C for 1 h [then trimethyl phosphite (5 mL) was added], then at 130 ° C for 2.5 h, maintaining the temperature of the distillation head below 40 ° C. The mixture was allowed to cool and the volatile fractions were removed under reduced pressure to leave an almost colorless liquid (21.65 g). After evaporation of this liquid portion (18.35 g), the oil was collected at 175-180 ° C (0.15 mbar), 78% pure by DC. Analytical sample purified using ethyl acetate: 60-80 ° C gasoline (2: 1) as eluent, ¹ H NMR (CDCl ₃ ): delta 3.43 (2H, d J 23Hz), 3.72 (d J 11 Hz) ) md

A solution of dimethyl 2-bromobenzylphosphonate (10.35 g) in dry DMF (50 mL) was added dropwise at room temperature to a stirred suspension of sodium hydride (0.979 g) in dry DMF (100 mL) (vigorous gas evolution). After 20 minutes, a solution of furfural (3.56 g) in dry DMF (50 mL) (exothermic reaction) was added and the resulting mixture was stirred at room temperature for 4 hours, then diluted with water and extracted with ether. The extracts were washed with water, treated with magnesium sulfate and charcoal, filtered, concentrated under reduced pressure and chromatographed using 40-60 ° C gasoline as eluent to give E-1- (2-furyl) -2- (2-bromophenyl) -. ethylene (3.755 g), a pale yellow liquid (containing about 6% DC of the corresponding Z-isomer).

This ethylene was converted to the title compound as described in Examples 1 and 3, namely by reaction of a magnesium derivative with dimethyloxalate and treatment of the resulting ketoester with methoxymethylenetrophenylphosphorane. The E, E-isomer eluted (elution) first in 30% ether in gasoline was an oil, IR (band): 1715 and 1637 cm ^-1 , ¹ H NMR (CDCl ₃ ): delta 3.68 (3H, s), 3 , 81 (3H, s), 6.31 (1H, d J 3.5 Hz), 6.40 (1H, dd J 3.5 and 2 Hz), 6.83 and 6.98 (1H, d each) J 16 Hz), 7.63 (1H, s) md; The Ζ, Ε -isomer was a solid, m.p. temp.

107.5-110 ° C, IR (nujol): 1717 and 1625 cm ^-1 , ¹ H NMR (CDCl ₃ ): delta 3.65 (3H, s), 3.93 (3H, s), 6.33 (1H, d J 3.5 Hz), 6.40 (1H, dd J 3.5 and 2 Hz), 6.56 (1H, s), 6.82 and 7.10 (1H, d_J each) 16 Hz) md

EXAMPLE

The emulsifiable concentrate was made by mixing the ingredients and stirring the mixture until all the ingredients had dissolved.

Example 5 Compound 10% Ethylene Dichloride 40% Calcium dodecylbenzene sulphate 5% Lubrol L 10% Aromasol H 35% EXAMPLE 13

A rapidly dispersible granular composition in a liquid, such as water, was obtained by mixing the first three ingredients together, adding water and mixing in sodium acetate. The resulting mixture was dried and passed through a 44-100 mesh sieve (British standard) to obtain the required grain size.

Example 3 Compound 50% Dispersol T. 25% Lubrol APN5 1.5% Sodium acetate 23.5%

EXAMPLE

All ingredients were ground together to form a powder that is readily dispersible in liquids.

Example 5 Compound 45% Dispersol T. 5% Lissapol NX 0.5% Cellofas B 600 2% Sodium acetate 47.5%

EXAMPLE

The active ingredient was dissolved in a solvent and the resulting liquid was sprayed onto kaolin beads. The solvent was allowed to evaporate to give a granular composition.

sample compound Kaolin granules

5%

95%

EXAMPLE

The composition suitable for seed dressing was obtained by mixing three ingredients.

sample compound 50%

Mineral oil 2%

Kaolin 48%

EXAMPLE

Dusias (dust powder) was obtained by mixing the active ingredient with talc.

sample compound 5%

95% Talc

EXAMPLE

Col's preparation was obtained by grinding the below components in a ball mill and slurrying the blended mixture with water.

Example 5 Compound 40% Dispersol T. 10% Lubrol APN 5 1% Water 49% EXAMPLE 19

The dispersible powder measure was prepared by thoroughly mixing the components listed below.

Example 3 Compound 25% Aerosol OT / B 2% Dispersol A.C. 5% Kaolin 28% Silica 40% EXAMPLE 20

This example illustrates the preparation of a dispersible powder measure. The ingredients were mixed and ground in a grinding mill.

sample compound

25%

Perminal BX 1% Dispersol T. 5% Polyvinylpyrrolidone 10% Silica 25% Kaolin 34% EXAMPLE 21

A dispersible powder was prepared by mixing and grinding the ingredients listed below.

Example 3 Compound 25% Aerosol OT / B 2% Dispersol A 5% Kaolin 68%

In Examples 12-21, the proportions of the ingredients are given as percentages by weight.

The compounds indicated in Tables 1, 2, 3, 4 and 5 are incorporated into the compositions in the same manner as described in Examples 12-21.

The following are explanations of trademarks and trade names of the compositions or substances used:

LUBROL L: Nonyl phenol (1 mol) condensate with ethylene oxide (13 mol)

AROMASOL H: mixture of alkylbenzene solvents

DISPERSOL T&AC: Sodium Sulfate and Formaldehyde Condensate with Sodium Naphthalene Sulfonate

LUBROL APN5: Nonyl phenol (1 mol) condensate with naphthalene oxide (5.5 mol)

CELLOFAS B600: Sodium carboxymethylcellulose thickener LISSAPOL NX: Nonyl phenol (1 mol) condensate with ethylene oxide (8 mol)

AEROSOL OT / B: Dioctyl Sodium Sulfosuccinate

PERMINAL BX: Sodium alkyl naphthalene sulfonate

EXAMPLE

The effects of the compounds on various plant fungal diseases were investigated. The following method was used.

The plants were grown in John Innes cup compost (# 1 or 2) in 4 cm diameter mini cups. Test compounds were incorporated into the formulations either by milling with aqueous Dispersol T, or as a solution in acetone or acetone / ethanol, which was diluted to the required concentration immediately prior to use. In the case of leaf diseases, compositions (100 ppm of active ingredient) were sprayed onto the leaves and applied to the roots of the plants in the soil. Sprays were applied to maximum leaf retention and soil treatment to a final concentration equivalent to about 40 m.d. active ingredient for dry soil. To obtain a final concentration of 0.05%, Tween 20 was added when the cereals were sprayed.

In most of the tests, the compounds were applied to the soil (root treatment) and applied to the leaves (spray) for a day or two after inoculation with the pathogen. An exception was the Erysiphe graminis test, where the plants were inoculated 24 hours before treatment. Leaf pathogens were sprayed with spore suspensions on leaves of test plants. After inoculation, the plants were placed in a suitable environment for the infection to develop and then incubated until the disease reached a suitable grade for evaluation. The time interval between inoculation and evaluation ranged from four to fourteen days, depending on the disease and the environment.

The control of disease development was recorded on the following scale:

= no disease = trace - 5% disease to untreated plants = 6- 25% disease to untreated plants = 26 - 59% disease to untreated plants = 60-100% disease to untreated plants

The results are shown in Tables 7, 8 and 9.

table

The data in this table are for the compounds of Table 1

Jun- ginio No. Puccinia recondita (wheat) Erysiphe grammatical hordes (barley) Venturia inaequalis (apples) Pyricularia oryzae (rice) Cercospora arachidicola (of land nuts) Plasmopara viticola (grapes) 1 4 4 4 0 2 4 2 2 0 0 0 0 0 3 0 0 0 0 0 4 4 0 0 1 0 0 0 5 0 0 0 0 0 1 7th 0 0 1 0 0 0 9th 4 4 4 3 * 4 4 10th 4 4 4 3 * 4 4 11th 0 0 0 0 0 3 12th 0 0 0 0 0 2 13th 4 2 4 2 4 4 14th 4 4 4 4 4 4 19th 4 4 4 3 0 4 20th 0 2 4 3 3 4 21st 0 4 0 0 4 4 22nd 0 0 0 0 0 4 23rd 4 0 0 0 4 4 24th 4 2 4 0 0 4 25th 2 0 0 0 - 3

* = studied by spraying leaves at 25 da.w. concentration.

table (continued)

Jun- ginio No. Puccinia recondita (wheat) Erysiphe grammatical hordes (barley) Venturia inaequalis (apples) Pyricularia oryzae (rice) Cercospora arachidicola (of land nuts) Plasmopara viticola (grapes) 26th 1 0 - 0 - 1 27th 3 2 4 2 2 4 28th 3 4 4 3 4 4 29th 2 3 4 0 0 3 30th 4 4 4 3 3 4 31st 0 4 2 0 0 3 32 3 0 3 1 3 0 35 0 2 0 2 4 0 40 4 4 4 4 4 4 42 3 4 4 4 1 4 52 4 1 4 4 3 4 53 0 0 4 0 2 4 54 0 0 - 0 - 0 55 0 0 * 4 3 1 * 4 * 56 4 0 * 4 4 0 * 4 * 57 3 0 - 4 - 0 58 0 0 0 0 - 3 60 4 3 4 4 4 4 61 3 0 2 2 - 4 66 0 3 0 0 - 0

* = studied by spraying leaves at 25 da.w. concentration.

table

The data in this table are for the compounds of Table 2

Jun- ginio No. Puccinia recondita (wheat) Erysiphe grammatical hordes (barley) Venturia inaequalis (apples) Pyricularia oryzae (rice) Cercospora arachidicola (of land nuts) Plasmopara viticola (grapes) 1 4 4 4 3 4 4 7th 4 4 4 4 4 4 66 3 4 4 0 0 3 153 4 4 4 0 3 4 160 0 4 4 3 4 4 161 0 0 4 0 3 * 3 177 4 4 4 2 4 4 180 0 0 4 0 0 3 181 4 * 0 * 0 * 0 * 0 * 0 *

* = studied by spraying leaves at 25 da.w. concentration.

table

The data in this table are for the compounds of Table 4

Jun- ginio No. Puccinia recondita (wheat) Erysiphe grammatical hordes (barley) Venturia inaequalis (apples) Pyricularia oryzae (rice) Cercospora arachidicola (of land nuts) Plasmopara viticola (grapes) 1 4 4 4 2 3 3 177 0 4 3 0 0 0

Claims (21)

DEFINITION OF INVENTION 1. Compounds of general formula (I): and stereoisomers thereof wherein X, Y and Z, which may be the same or different, are hydrogen or halogen, or optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl, optionally substituted alkynyl, haloalkyl, alkoxy, haloalkoxy, optionally substituted aryloxy , optionally substituted arylalkoxy, optionally substituted acyloxy, optionally substituted amine, optionally substituted arylazo, acylamine, nitro, nitrile, -CO ₂ R ³ , -CONR ⁴ R ⁵ , -COR ⁶ , -CR ⁷ = NR ⁸ or -N = CR ⁹ R ¹⁰ groups; or the groups X and Y, when adjacent to the phenyl ring, may be bonded to form a fused ring, or an aromatic or aliphatic, optionally containing one or more heteroatoms; and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ , which may be the same or different, are hydrogen or alkyl, cycloalkyl, alkenyl, alkynyl, optionally substituted aryl, optionally substituted aralkyl, or cycloalkylalkyl; and their metal complexes. Compounds according to claim 1, characterized in that they have the general formula (I): and stereoisomers thereof wherein X, Y and Z, which may be the same or different, are hydrogen or halogen, or optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl, optionally substituted alkynyl, haloalkyl, alkoxy, haloalkoxy, optionally substituted aryloxy , optionally substituted arylalkoxy, optionally substituted acyloxy, optionally substituted amine, acylamine, nitro, nitrile, -CO 2 R ³ , -CONR ⁴ R ⁵ or -COR ⁶ groups, or X and Y groups when adjacent to the phenyl ring forming a fused ring, or an aromatic or aliphatic ring optionally containing one or more heteroatoms; and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ , which may be the same or different, are hydrogen or alkyl, cycloalkyl, alkenyl, alkynyl, optionally substituted aryl, optionally substituted aralkyl or cycloalkylalkyl; and their metal complexes. Compounds according to claim 1 or 2, characterized in that they have the general formula (I): CH OR ² O) and stereoisomers thereof wherein X, Y and Z, which may be the same or different, are hydrogen or halogen, or optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl, optionally substituted alkynyl, haloalkyl, alkoxy, haloalkoxy, optionally substituted aryloxy, optionally substituted arylalkoxy, amine, acylamine, nitro, nitrile, -CO ₂ R ³ , -CONR ⁴ R ⁵ or -COR ⁶ ; and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ , which may be the same or different, are hydrogen or alkyl, cycloalkylalkenyl, alkynyl, optionally substituted aryl, optionally substituted aralkyl, or cycloalkylalkyl; and their metal complexes. Compounds according to any one of claims 1 to 3, characterized in that they have the general formula (I): and stereoisomers thereof wherein X, Y and Z, which may be the same or different, are hydrogen or halogen, or optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl, optionally substituted alkynyl, haloalkyl, alkoxy, optionally substituted aryloxy, optionally substituted arylalkoxy, optionally substituted amine, the groups -CO 2 R ³ or -COR ⁶ , or the groups X and Y which are adjacent to the phenyl ring, may be bonded to form an aromatic fused ring; and R ¹ , R ² , R ³ and R ⁶ , which may be the same or different, are alkyl, optionally substituted phenyl, or optionally substituted aralkyl. Compounds according to any one of claims 1 to 4, characterized in that they have the general formula (I): and stereoisomers thereof, wherein X, Y and Z, which are identical or different, are hydrogen, fluorine, chlorine or bromine atoms or C _1-4 alkyl, C _2-5 alkenyl, C2-5alkinilo, phenyl, Ci- ₄ haloalkyl, , C 1-4 alkoxy, phenoxy, benzyloxy or mono- or dialkylamino groups, or groups X and Y, when adjacent to the phenyl ring, may be bonded to form a fused aromatic ring, aliphatic moieties of any of the above groups being optionally substituted by one or more Ci- ₄ alkoxy group, fluorine, chlorine or bromine atoms, phenyl rings which themselves are optionally substituted, heterocyclic rings which are either aromatic or non-aromatic and are themselves optionally substituted with nitro, amino, nitrile, hydroxyl or carboxyl groups; and wherein any of the above components of the phenyl is optionally substituted by one or more fluorine, chlorine or bromine atoms, phenyl rings, Ci- ₄ alkyl, C ^ alkoxy, nitro, amino, nitrile, hydroxyl or carboxyl groups; R ¹ and R ² , which may be the same or different, are C _1-4 alkyl, phenyl or benzyl groups, each optionally substituted by halogen. Compounds according to any one of the preceding claims, characterized in that they have the general formula (XI): wherein R is optionally substituted phenyl or optionally substituted benzyl and Y is a hydrogen or halogen (fluorine, chlorine or bromine) atom or a methyl, methoxyl, nitro, nitrile, carboxyl or methoxycarbonyl group. Compounds according to any one of claims 1 to 5, characterized in that they have the general formula (XII): (XII) and stereoisomers thereof, wherein X is an alkyl, alkenyl, alkynyl, aryloxy or arylalkoxy group, each of which is optionally substituted. Compounds according to any one of the preceding claims, characterized in that they have the general formula (XIII): (XIII) and stereoisomers thereof, wherein X is a group of optionally substituted alkyl, optionally substituted alkenyl or optionally substituted alkynyl. 9. Compounds according to claim 8, characterized in that the possible substituents are phenyl optionally substituted by one or more of the following substituents: fluorine, chlorine, bromine, Ci. ₄ alkyl (especially methyl), C _1-4 alkoxy (especially methoxy) or nitro groups. Compounds according to any one of claims 1 to 7, characterized in that they have the general formula (XIV): and stereoisomers thereof wherein X is a optionally substituted aryloxy group or a potentially substituted arylalkoxy group. 11. Compounds according to claim 10, wherein X is phenoxy or benzyloxy, both optionally substituted with one or more halogen (fluorine, chlorine or bromine), or methyl, methoxyl, ethyl, ethoxyl, nitro, nitrile, carboxyl or methoxycarbonyl. . Compounds according to claim 11, characterized in that they have the general formula (XV): (XV) and stereoisomers thereof wherein X, Y and Z, which may be the same or different, are fluorine, chlorine, bromine or hydrogen, or methyl, methoxy or nitro. Compounds according to any one of claims 1 to 12, characterized in that they have the following specific structure: a) H OCH ₃ (compound 9 in Table 1) b) OCH 3 (compound 13 in Table 1). (Compound 19 in Table 1). d) OCH ₃ (compound 1 in Table 2) θ) H (compound 1 in Table 4) Process for the preparation of compounds according to any one of claims 1 to 13, characterized in that the compound (II) of the general formula (II). wherein R ¹ , X, Y and Z are as defined in any one of the preceding claims, but R ¹ is not a hydrogen atom, reacting with a compound of the general formula (V): + Ph ₃ P.CHOR ² (V) wherein R ² is as defined in any one of the preceding claims but is not a hydrogen atom. 15. A process for the preparation of compounds according to any one of claims 1 to 13, wherein the compound of the general formula (VII): ch ₂ co ₂ r ¹ (VII) wherein X, Y, Z and R ¹ are as defined in any one of the preceding claims but R ¹ is not a hydrogen atom, reacts with a base and a compound of the general formula HCO ² R ¹ , wherein R ¹ is as defined in any one of the preceding claims, but is not a hydrogen atom, and then in the same reaction vessel or in a separate step in the presence of a base, the resulting materials react with a compound of general formula R ² Q ² is as defined in any one of the preceding claims, and Q is a leaving group such as, for example, a halogen atom. 16. A process for the preparation of compounds according to any one of claims 1 to 13, wherein the compound of the general formula (VIII): Z (VIII) wherein R ¹ , R ² , X, Y and Z are as defined in any one of the preceding claims, is reacted with a suitable acidic or basic reagent. Novel intermediates of formula (II) and (VIII). 18. A pesticidal or plant growth regulating composition comprising the active ingredient and a suitable carrier, wherein the active ingredient is a compound according to any one of claims 1 to 13. 19. The composition of claim 18, which is a fungicidal composition. A method of controlling pests, especially fungi, wherein the plants, plant seeds or plant seed locations are treated with a compound according to any one of claims 1 to 13 or a composition according to claims 18 or 19. Use of a method according to claim 20 for killing weeds or harmful insects, or for regulating plant growth.