PH26120A

PH26120A - Aryloxycarboxylic acid derivatives the preparation and use thereof

Info

Publication number: PH26120A
Application number: PH38179A
Authority: PH
Inventors: Wolfgang Buck; Erich Raddatz
Original assignee: Shell Agrar Gmbh & Co Kg
Priority date: 1989-02-10
Filing date: 1989-02-10
Publication date: 1992-02-24

Description

pa -_— ’ . , 26120 vo - 2 -

The invention relates to new agents for combating : phytopathogenic fungi, new active substances for these agents and processes for .preparing the active substances.

The compounds which may be used in the new agents correspond to formula I

Ri Ra

Aryl - Xx - Q - CON - ¢ - Ry (1).

Ry

In formula I and hereinafter:

Aryl represents a phenyl group, either unsubstituted or mono- to tri-substituted by C;_g alkyl,

Ci-5 alkoxy, Cy_g alkyl-SO, (n =0, 1 or

Lo 2), halogen, NO,, CFg3/ CN, CH40CH,, (CH4) 5NCH,,

CcoOalkyl, CONH, or phenyl; a 1- or 2-naphthyl - group; an optionally chlorine-substituted 2-, 3- : or 4-pyridyl group; a pyrimidyl or quinolyl group,

Rg

Q represents - ¢ - (CH,) o (m = 0, 1 or 2) i Rg if represents H, Cy _g alkyl, allyl, . R, and Ry represent H, C, _¢ alkyl (which may also contain an O or S atom in the chain), phenyl, C; , cycloalkyl, CH,-CO0-(Cy_g alkyl),

R, and Rq together may also represent —(CHy) 4

CH,

R, represents CN, CONH, /

Re represents H, CH,, C,He, .

Re represents H, CHq, . !

-2- 26120

X represents O or S. 1f the compounds of formula I contain asymmetric carbon atoms these compounds may occur in the form of their individual enantiomers or mixtures thereof.

If the substituents R; to Rg contain hydrocarbon chains, these may be straight or branched and may be identical to or different from one another. chains with up to 4, more particularly up to 3 carbon atoms are preferred. The preferred alkyl substituent in the aryl group is CH,. Halogen represents fluorine, chlorine, bromine or iodine, preferably chlorine and fluorine. The substituents : in the aryl group may be jdentical or different.

CF, CN, NO,, (CH) ,NCH,, phenyl and Cis alkyl- 80, generally occur only once. If aryl represents a quinolinyl group it is preferably 8-quinolinyl.

The majority of compounds of formula I are new; they are prepared in known manner. . : 1. Reaction of compounds of formula : | Aryl - Xx - Q - COY (11) wherein aryl, X and Q are defined as hereinbefore } and Y represents a leaving group, e.g. halogen: (preferably chlorine), o-alkyl, OH, acyl, : with a compound of formula

Ry Ra

HN - C - R, (III) i ,

Ry wherein Ry - R, are defined as hereinbefore,

. , 20120 -.4 - thereby eliminating HY.

The reaction is preferably carried out in an inert solvent, e.g. methylene chloride, toluene, acetonitrile, an ether, or in a mixture of solvents at temperatures of between ambient temperature and the boiling temperature : of the reaction mixture, whilst the reaction will be promoted by an HY-binding agent, : for example a base if HY represents an acid such as HCl, dicyclohexylcarbodiimide or carbonyldiimidazole if HY represents water.

The starting materials are known or may easily be prepared by conventional methods. Thus, compounds of formula II wherein

Y = OH may be obtained for example by reacting corresponding phenols or thiophenols (aryl-XH) : with ethyl 2-bromopropionate in the presence of a base and subsequent hydrolysis of the ester. From the carboxylic acids thus obtained, the corresponding carboxylic acid chlorides of formula II are formed, e.g. by reacting with thionyl chloride.

The a-amino acid nitriles (III, R, = CN), may be prepared by Strecker synthesis from the corresponding ketone or aldehyde, NaCN : and NH,Cl in water (Houben-Weyl, Vol. VIII, page 274ff (1952)). The a-amino acid amides (III, Ry = CONH,) are obtained from the corres- ponding nitriles by partial hydrolysis. 2. Reaction of a compound of formula

Aryl - XM (IV)

A

26120 1. - 5 — 0 wherein aryl and X are defined as hereinbefore and M indicates hydrogen or an alkali metal . cation, with a compound of formula {Ra z2-Q-CON - C - Ry (v)

Ry oo wherein Ry to R, and Q are defined as hereinbefore and Z represents halogen or an arylsulphonyloxy group.

The reaction is carried out in an inert polar solvent. If M = H, a base is added. Conditions under which a compound IV wherein M = K or

Na is formed are preferred.

The preferred definitions of Zz are bromine and CH4-CgH,-SO5 . whilst the preferred solvent is acetonitrile. }

The reaction is carried out at elevated temperatures, e.g. at reflux temperature. Suitable bases include, for example, alkali metal carbonates, alkali metal hydroxides, and optionally also sufficiently basic : amines such as triethylamine. \

Depending on the definitions of R, to Res compounds ) of formula I with one or two centres of asymmetry : may occur. The isomers may, {f desired, be separated ‘ by conventional methods or synthesised directly . by using optically active starting products.

’ f ~ . ) -6 - 26120 . . ' { : CH 1.3

HO-C H-COOAlkyl (-) ns{O)- we AN PBR,

Gi: ot . CH, $0,-0-C H-COOAlkyl Br-C H-COOAlkyl (-) (+)

Ar -OH Ac-OH

Gs oe ) Ac-o-¢ H-COOAlkyl Ar-0-C H-COOAlkyl (+) (-) :

NaOH: HCl | NaOH: HCl

CH CH

[a3 [a3

Ar-0-C H-COOH Ar-0-C H-COOH (+) (=) . soci, or soci, or

Cl1-CO-CO-Cl . Cl-COo-co-Cl1

CHy ° CHy 0

Ac-0-¢"i-c © EN (-) Cl (+) Cl ’ (11), (-) form (I1), (+) form "mlkyl" preferably represents methyl or ethyl

: t+ + ' 4 a 26120

Similar steps lead to optically active starting materials of formula V; in this case, too, other optically active compounds of formula V may be obtained accordingly.

CH

1.3

HO-C H-COOAlkyl (-) cty{O)-s0yc1 is cty{O)-s020-¢ H-COOAlkyl ¢ (-) ¢ Jeo HC1 is

CH, O §0,0-C H-COOH (-)

I.

CH 0

CH 50.0 Lac? 3 O 27 \ (+) Cl

BR,

En Co :

R

4 \ [2 2

CH, O $0,0- H-CO-NR, -C-R, (-) R, ; fo (Vy, (-) form

The compounds of formula I have a fungitoxic effect on phytopathogenic fungi. They may be used particularly against fungal diseases in rice. Although the new compounds are partly derived from herbicides (Dichlorprop., 2,4-DB) they are surprisingly well Co tolerated by plants.

For use, the compounds of formula I are processed - with conventional excipients and/or carriers to produce the usual preparations which are diluted for use in the form of a spray liquor with suitable quantities of water. Preparations of this kind include, for example, emulsifiable and soluble concentrates, wettable powders, dusting powders and granules which may contain up to 80% by weight of active substance. Lo

Examples of formulations: 1. Emulsifiable concentrate. 5.0 parts by weight of active substance : according to the invention 3.4 parts by weight of epoxidised veg: table oil 13.4 parts by weight of a combined emulsifier : of fatty alcohol polyglycol- } ether and calcium alkylarylsulphonat 40.0 parts by weight of dimethylformamide 38.2 parts by weight of xylene

The components are mixed together and, for application, diluted with water to give a concentration of active substance of 0.01 to 0.1% by weight.

Y

BAD ORIGINAL J)

. Co

Wettable powder & . . 10 parts by weight of active substance according to the invention 3 parts by weight of sodium fatty alcohol sulphonate parts by weight of salts of naphthalene sulphonic acid-formaldehyde condensate 82 parts by weight of kaolin

The activity of the compounds according to the invention, e.g. against Piricularia, was tested on rice seed under tropical conditions. 2 rows . of rice seed (I and II) between older rows naturally infected with Piricularia were treated on the 41st, 45th and 49th day after sowing with spray liquors ¥ containing specific quantities of active substance.

The control treated only with water was used as a comparison. The results were graded 6, 8, 10 : and 13 days after the last spraying (% of plants attacked).

The compounds according to the invention proved highly effective against Piricularia and well tolerated by the plants.

Additional tests are described hereinafter.

Lod

Effect against Piricularia in rice

A. Leaf treatment

Rice plants were first grown in propagation trays.

They were sprayed until dripping wet with emulsions or suspensions containing 1000, 500 or 250 ppm of the active substance in question. Two days after treatment the propagation trays were left in che open between infected rice plants for 5-6 days to allow infection to occur. Findings were evaluated 5-8 days later.

B. Soil treatment oo

Rice plants were first grown in flower pots. Emulsions or suspensions containing 500 ppm of the active substances specified were poured onto the roots.

Two days after treatment the pots were left in ’ the open for 4-6 days between rice plants infected with Piricularia in order to allow infection to occur. The results were evaluated 5-7 days after the infection.

The findings were graded 1 to 3: 1: no attack 2: slight attack ’ 3. attack similar to that of the untreated control. \ The numbers given in the Table are averages from 3 tests and several grades awarded at different times. ,

C. Application under water (submerged application)

Rice plants were planted in earth-filled buckets. water was added until it formed an unbroken covering over the earth. A quantity of active substance was added in the form of a suspension or emulsion : to correspond to an application of 8 or 4 or 2 kg/ha a.i.™ 2 days after treatment the test plants were left in the open between infested rice plants and remained exposed to infection throughout the experiment.

The results were evaluated one day after attack had occurred on the untreated control and the evaluation was carried out 4-5 times (3 experiments with each } substance). Evaluation was as in A and B. The numbers in the table are the averages from three experiments and several grades. > active ingredient

Test results

Active Concentration Number of attacks substance | of active Test C : according | substance Test A Test B Number of to [ppm] kg/ha Attacks

Example

Tab. II 1000 1.0

No. 62 500 1.0 1.8 2.0 250 : 1.0

Example 1000 1.0 4 1.8

No. 9 - 500 1.0 2.0 2 2.2 250 1.5 ) .

Tab. II 1000 - ’

No. 1 500 1.0 2.5 8 1.8 © 250 1.0

Tab. V 1000 1.0 :

No. 2 500 1.5 1.0 1.5 ° 250 2.5

Example 1000 1.0 1.8

No. 4 500 1.8 2.1 : 250 2.1

Tab. II 1000 1.1

No. 2 500 1.0 2.0 250 2.0

Tab. II | 1000 1.0 . No. 33 500 1.0 250 i 2.0

Example 1000 1.5

No. 6e 500 2.0 2.0 250 2.0

Tab. IV 1000 -

No. 6 500 1.0 1.9 250 1.0 :

26120 + - 13 -

Example 1 2-'(2,4-Dichlorophenoxy) propionic acid-N-(l-ethyl- l-cyanopropyl) -amide '

C1 03 - Falls

Cl O - CH - CONH- C - C_H { 25

CN . ‘ 2.2 g of 3-amino-3-~cyanopentane and 2.4 g of triethylamine are dissolved in 100 ‘ml of methylene chloride. : 5.1 g of 2-(2,4-dichlorophenoxy)-propionic acid chloride are added and the mixture is stirred overnight ’ at ambient temperature. The solution is extracted with water and sodium hydrogen carbonate solution, dried and evaporated down. The residue obtained consists of 6.3 g (96% of theory) of a brownish viscous oil which crystallises when stirred with diisopropylether.

Yield: 4.9 g of white solids (74% of theory)

Melting point: 100 - 102°C

The structure is confirmed by spectroscopic investigation.

Analysis: CygH gCLl,N,0, M = 329.23

Cs HS CLs Ne ‘ Found: 54.58 5.54 21.06 8.35

Calculated: 54.72 5.51 21.54 8.51

Example 2 a 2- (4-Methylthiophenyloxy)~propionic acid-N-(l-cyano- 1,2-dimethylpropyl)-amide

CH CH, CH

Tr 3 3 3

CH,S O - CH - CONH - ¢ Zc ’ & “cu 3 2.5 g of 2-bromopropionic acid-N-(l1-cyano-1,2-dimethyl- propyl) -amide (prepared analogously to Example 5a) and 1.4 g of 4-methylmercaptophenol are dissolved in 50 ml of methylisobutylketone. After the addition of 1.5 g of potash the mixture is stirred for. 3 hours at 80°C. The solution is suction filtered and evaporated down. 2.8 g of brownish oil are ‘ obtained (91.5%) which crystallises when stirred with diisopropylether.

M.p. 83-86°C

Analysis: C,gHgoN,025 M = 306.43

C3 H% N% S%

Found: 62.48 7.24 9.23 10.34

Lo Calculated: 62.71 7.24 9.14 10.46 ’ The structure was confirmed by spectroscopy.

Example 3 2- (4-Chloro-2-methylphenoxy) -propionic acid-N-[3- cyanopent-3-yl]-amide 4.4 g of 2-amino-2-ethylbutyronitrile (0.039 mol) and 4.6 g of triethylamine (0.046 mol) are dissolved

-_ -— — _ — 26120 - 15 =- in methylene chloride, 9.0 g of 2- (4-chloro-2-methyl- phenoxy) -propionic acid chloride (0.039 mol) are added dropwise with stirring. The mixture heats up. It is stirred for a further 3 hours without heating, extracted successively with water and bicarbonate solution, then dried and evaporated down. The residue obtained consists of a brown oil (10.8 g) which crystallises when stirred with - isopropylether. The product is suction filtered and dried. : yield: 10.6 g (88% of theory) of white solids

M.p.: 125 - 126°C.

Elemental analysis and NMR spectrum confirm the formula given. : r Example 4 2-(4-Chloro-2-methylphenoxy) -propionic acid-N-{2- cyano-3-methylbut-2-yl]-amide

Analogously to Example 3 the title compound is obtained from equimolar quantities of 2-amino-2,3- dimethylbutyronitrile.

Bh Yield: 76% of theory; m.p.: 97 - 99°C.

The product is initially obtained as a brown oil.

It consists of 4 isomers. The mixture can be resolved into 3 fractions by step-wise precipitation with cold ether. "

From 11.1 g of oil are obtained:

Fraction I: 1.8 g of white solids m.p.: 117-118°C;

Fraction II: 1.8 g of brownish solids = oe m.p.: 94-96°C;

Fraction III: 5.6 g of reddish oil (purified by chromatography)

NMR spectroscopy indicates enrichment of the pairs of enantiomers in Fractions I and II:

Fraction I Enantiomeric pair I to enantiomeric pair II 89 : 11 (diastereomeric ratio)

Fraction II Enantiomeric pair I to enantiomeric . pair II 26 : 74 ~The pairs of enantiomers may be further concentrated by recrystallising the fractions.

. . . . i ’ 1 26120 - 17 -

The following compounds of the following formula are also obtained in accordance with the preceding

Examples:

CH, 0 fi Te

Cl— 0-QCON - ¢ - Ry . Ra . . Table I

No. Q . Rg Rj. Ry Ry Mp. [°C] 1 CH, C,H, C,H H CN 86-88 2 CH(CH,) i-c H, CH, H CONH, 108-111 3 CH, i-cyH, CH, H CONH,, 105-107 4 CH, i-c,H, CH, H CN 102-103 s CH(CH,) n-C,H, CH, H CN 71-75 6 CH(CHy) C,H, | cH, H CN 86-87

C7 CH(CH,) n-C,H, CH, H CONH 100-102 8 CH(CH,) n-CcH,, CH, H CN . 9 CH(CH,) - (CH) g- H CN 134-136 oo 10 CH, -(CH,) H CN 118-120 11 CH, i-c H, CH, CH, CN 12 CH(CH,) i-C H, CH, CH, CN Oil

I3 CH (CH, -(CH,) ,- .. H CN 143-146 14 CH(CH,) “(CHa H CN 121-127

Co : CH,

06120 - 18 - : | Example 5 oo 2-(4-Chlorophenylthio) -propionic acid-N-(l-ethyl- l-cyanopropyl) —amide a) 2-Bromopropionic acid-N-(l-ethyl-l-cyanopropyl)- amide

C_H CN 2S

Ne” cH, cu” Nuc - cH n \ ‘ oO Br 36.5 g of 2-amino-2-cyano-n-pentane in 100 ml : of methylene chloride are added dropwise, with stirring, over a period of 40 minutes, to 88.4 g of 2-bromopropionic acid anhydride (0.325 mol) dissolved in 280 ml of methylene chloride.

After stirring overnight, the solu:ion is extracted with water and sodium bicarbonate solution, dried and evaporated down. The remaining oil is triturated with a little ether whereupon the product crystallises out.

M.p. 85-87°C

Yield: 61.2 g (76.5% of theory) ’ b) oo

CH, TMs

Cl s - Luconn Sc cm i 2's ’ : CN . 5.8 g of 4-chlorothiophenol (0.04 mol) are stirred in 150 ml of methylisobutylketone with 12.2 g of potassium carbonate at 90°C for 10 minutes. 9.9 g of 2-bromopropionic acid-N-(l-ethyl-1-

cyanopropyl) -amide are added to the resulting suspension with stirring and the mixture is stirred for another 5 hours at about 9p°C.

The solution is filtered, extracted successively with water, 2N sodium hydroxide solution and water, dried with magnesium sulphate and evaporated down. A brown oil is obtained which hardens to form a brownish crystalline mass when stirred - with a little ether.

M.pP. 108-110°C vield: 7.2 g (58.1% of theory)

Elemental analysis

C H N Cl S calc.: 57.96% 6.16% 9.01% 11.4% 10.32% Lo

Found: 57.77% 6.35% 8.86% 11.32% 10.28% : The following compound is also obtained according to the preceding Example

Hs - 0 - - Cc 10) CHE NH ¢ CH ( Hy), .

CH CN

. } 3

M.p.: 106-109°C.

Example 6 i (+) -2- (4—Chloro-2-methylphenoxy) -propionic acid-

N-(l-ethyl-1-cyanopropyl) -amide a) Methyl (-)-0- (4-methylphenylsulphonyl)-lactate 26.9 g of triethylamine are added dropwise to a solution of 25.2 g of methyl S-(-)-lactate : and 46.1 g of p-toluenesulphonic acid chloride

_—_———— _ . _. — 1 26120 - 20 - in 160 ml of toluene. The mixture is stirred overnight and the precipitate is removed by suction filtering. The toluene solution is extracted with dilute hydrochloric acid and water, dried with sodium sulphate and evaporated down. 55.9 g of colourless oil are obtained, . which is purified by vacuum distillation.

B.p.y 5: 148-152°C [a]3!: -50.1° (ethanol)

Yield: 43.5 g (70% of theory) : b) Methyl (+)-(4-chloro-2-methylphenoxy)-propionate 41.9 g of methyl S-(-)-0-(4-methylsulphonyl)~ lactate and 23.1 g of 4-chloro-2-methylphenol are dissolved in 100 ml of acetonitrile, 50 g : of potash are added and the mixture is refluxed for 10 hours with stirring. The solution is suction filtered and evaporated down. The residue is taken up in toluene, extracted with IN sodium hydroxide solution, dried and concentrated by evaporation. 32.2 g of reddish liquic¢ are obtained (87% of theory) c) (+)-4-Chloro-2-methylphenoxypropionic acid “The crude product obtained in b) (32.2 g) is dissolved in 100 ml of acetone. A solution of 6.8 g of NaOH in 30 ml of water is added : . dropwise with stirring and while cooling with ice. After stirring overnight the mixture is diluted with water and extracted with methylene chloride. The aqueous solution is acidified with conc. hydrochloric acid and the product : precipitated is extracted with methylene chloride.

The methylene chloride solution is separated off, dried and evaporated down. An oily residue is obtained which solidifies immediately.

M.p.: 62-72°C (pressed onto clay) (a124: + 14.1° (ethanol) vield: 27.7 g (91% of theory) d) (-) -4-Chloro-2-methylphenoxypropionic acid chloride 27.2 g of (+) -4-chloro-2-methylphenoxypropionic acid and 30.2 g of thionyl chloride are stirred with 100 ml of toluene for 3 hours at 100°C. - The solution is evaporated down in vacuo. 29.6 g . of brown oil are obtained, which is reacted without purification. e) (+) -2- (4-Chloro-2-methylphenoxy) -propionic acid-

N- (1-ethyl-1-cyanopropyl) -amide 8.4 g of the crude product from 4d) are added dropwise to 4 g of 3-amino-3-cyano-n-pentane and 4.4 g of triethylamine, dissolved in 100 ml of toluene, at -20 to -30°C with stirring.

The mixture is then stirred for 3 hours at RT, extracted with water and the solution is evaporated down. The oily residue (8.8 g) is stirred with diisopropylether, whereupon a crystalline product is precipitated and then separated off. vield: 2.8 g (25% of theory)

M.p.: 98-100°C (a1? + 9.1° (ethanol)

Example 7 (=)-2-(4-Chloro-2-methylylphenoxy) -propionic acid-

N-(l-ethyl-l-cyanopropyl)-amide a) Ethyl (+)-2-bromopropionate 47.2 g of ethyl S-(-)-lactate are dissolved in 300 ml of methylene chloride. 108 g of phosphorus tribromide are added dropwise. The reaction is exothermic. After stirring overnight at

RT the mixture is poured onto ice and stirred with water. The methylene chloride solution is extracted with bicarbonate solution, dried and evaporated down. The residue is distilled. 2 “ vield: 33.8 g; colourless oil (47% of theory)

BPys mbar 55-56 °C. b) Ethyl (-) - (4-chloro-2-methylphenoxy)-propionate

The product described in a) (33.8 g) is dissolved together with 26.7 g of 4-chloro-2-methylphenol in 300 ml of toluene and after the addition of 52 g of K,CO; it is refluxed for 10 hours ’ with stirring. The solution is suction filtered, extracted twice with 1N sodium hydroxide solution, " dried and evaporated down. 34.3 g of clear liquid are obtained (76% of theory) [a122: -14.46° (ethanol) ¢) (-)-(4-Chloro-2-methylphenoxy)-propionic acid ( (-) -CMPP) - Hydrolysis of the ester obtained in b) is carried out as in Example 6c).

From 24.2 g of ethyl (-)-(4-chloro-2-methylphenoxy)- propionate, 19.7 g of (-)-(4-chloro-2-methylphenoxy)- propionic acid are obtained (92% of theory). arp = dP —-

M.p.: 69-75°C la]22: -9.679° (ethanol) ad) (+) - (4-Chloro-2-methylphenoxy) -propionic acid chloride ( (+) -CMPP-chloride)

The acid described in 7c) is converted analogously to Example 6d) into the acid chloride which : is further processed without purification.

From 8.6 g of (-)-CMPP, 8.4 g of (+)-CMPP chloride is obtained as a brownish oil (90% of theory) 22 ° (alg + +4.486 (CCl,) e) (=) -2- (4-Chloro-2-methylphenoxy) -propionic acid-

N-(l-ethyl-l-cyanopropyl)-amide

The (+)-CMPP chloride is reacted with 3-amino- : 3-cyano-n-pentane as described in Example 6e). 3 g of (-) -2- (4-chloro-2-methylphenoxy) -propionic acid~N- (l-ethyl-l-cyanopropyl) -amide are obtained (28% of theory) from 8 gq of (+)-CMPP chloride.

M.p.: 98-100°C , [a12%: -8.584° (ethanol)

A variant for the preparation of the dextrorotatory phenoxypropionic acid amides is described hereinafter taking a~ an example (+) -2- (4-chloro-2-methylphenoxy)- propionic: acid-N-(l-ethyl-l-cyanopropyl) -amide:

Example 8 (+) —2- (4—Chloro-2-methylphenoxy) propionic acid-

N-(l-ethyl-l-cyanopropyl) -amide a) (+) -O- (4-Methylphenylsulphonyl) -lactic acid chloride be Cw

17.9 g of (-) -0- (4-methylphenylsulphonyl) -lactic acid (Helv. Chim. Acta 65/1240 (1982)) and 13 g of thionyl chloride are stirred at 95-100°C for 3 hours. The product is evaporated down in vacuo and degassed. 19.2 g of brown oil are obtained (100% of theory). b) (-) -O- (4-Methylsulphonyl)-lactic acid-N-(l-ethyl- 1-cyanopropyl) -amide 18.8 g of the crude product from Ba) are added dropwise at -20 to -30°C to a solution of 8 g of 3-amino-3-cyano-n-pentane and 8.8 g of triethyl- amine in 200 ml of toluene. The mixture is i ‘stirred for 3 hours at -20°C and then overnight at RT. The solution is extracted with water and evaporated down. 23.4 g of brown clear oil are obtained (96% of theory) which is crystallised by stirring with diisopropylether.

M.p.: 57-60°C [a]2? -40.4° (ethanol) vield: 8.4 g (34% of theory) c) (+) -2- (4-Chloro-2-methylphenoxy) -propionic acid-

N- (l-ethyl-l-cyanopropyl)-amide 4.7 g of (-)} -O- (4-methylsulphonyl) -lactic acid

N-(l-ethyl-l-cyanopropyl)-amide and 2 g of 4-

Co chloro-2-methylphenol are dissolved in 100 ml . of toluene. 4.5 g of powdered potash are added and the mixture is refluxed for 12 hours with stirring. The solution is suction filtered, extracted with 1N sodium hydroxide solution and evaporated down. 3.1 g of yellow oil are obtained (72% of theory) which crystallises when stirred with diisopropylether. 2.2 g of white crystalline solids are obtained (51% of theory).

M.p.: 97-99°C [a]2?: +11.94° (ethanol)

In accordance with Examples 6 to 8, the dextro- and levorotatory enantiomers of the following compound ’ are also prepared: cs

THs Hi : {Oy - CHCONH - ¢ - CH(CH,), : CN

Example 9: [a)2? = 9,1° : (ethanol) oils, mixtures of diastereomers

Example 10: (a]2? = -7.65° (ethanol) /

EEE eee -—-— v . 1! . - v ’ : \ t 26 ' — ~ «tr

Q Q <r ° o — — ~ ©o - © t ' O° ~ . ' w ~ o~ a. on oO — «tr 0 ar ~ — o — © ~ = o (ia) oy oy on oN “© x x= x x x x ot ww QQ |] QQ QQ QQ wv [+] x = x x x x . -r = = = = = = ‘ ot QQ QO 0 QO QD QQ . oN — . « ~ oN «" — — 4. xs oy [2a — oO x x = = © a) [¥] vy =x = x ~ © ©

Pa x oN x ! oN xt |S] . QL oO o x . . QQ ~ x } | 8) po. ' oo Ln

Co o~ x= oN x [8] ] . og—O— Od ~

Lan] : ' = ' : ’ ~— [3 of —- 2 3 ' o o Pa) ™ oy oN > x x x= x 0 S ox |] |) |] oO <Q

Ig

So — ! - Fa) ©

Ee gE @-o-o 1%] ' . ’ 0 ~~

Uy o — = x x x oO x x x

Gy 1 , 0 —_ '

Sn

Cs aE co i» o 3 * ' 3 .

Q, — = : : z : g B . — 0 < IS . O — ou a < “ © x= !

. . s . 27 — Pp

Q —- = ° wy “w — , “a ~ : &~ ~ \ — — . ! ! o~ ~ i o 2 = — o a Q ' &~ t~ — — = mn m m © oy oy - © x > - xe foo) - x= [=] [8] QQ oO Q I) oS S f i - [] ox: x3 x x x x x: x ; . ! 1 - © me = = = > - = ot 0 oO Oo 0 O S S oN ~ . “a — — x faa) Lal oN x x= od [al [&)

S] oO — x S — - - S - x x x Oo [3]

S] [&] QL oN oN oN oN ~~ x x . ~ x x : x |] [3] . o= © | J oO 1 - 1 ( < [ _ - oN — x oN © x ~ | & 1 . = ’ Lo ' —_ la) = ’ OS * . = a OQ x laa) La) 1 Lia) oN og _- x i", og |& | x= OO QQ ~~ . . os xz x= x x x x = »> or 0 r ca = = z z z = [59 — -< (8) » 2 ~ wo on o —_ ~ - = . — —— — Co .

: - ) * + 28

QO

° [oS 0 o~ —4 «Fr = % % ® - = ~ Ss 1 a. w et o o pa ™ © s 00 on “ © Oo I.) ~ _ [a] y [a] oo ™

Oo x x x x .- ~ of - x x= x | & | & Qo oo | 8] 1 x x x= x x= x x= x ' a = = = = : = = = = [= . QO QQ |] |S} |S] Oo QQ [&] . oN -

Lal o~ o~ od x= — —_— — — QQ oN oo [al ~4 So x x xo x oxo ’

S) La] Q L [a] « QQ

S— = — — x= © oN [al x oN x = oN ! b=] ox oO © oO oO © c oO ' wv . o~ x © “ . 1 wy “wy [al = la) a) x [2a] laa) oN x= [a] x xe oN x = ox QO oO Oo L LQ QO QO [a] ~ = ox = x x x oO x x x 1 . = ©) z = : = : z to — < QO . 2 hd oy 0 ~~ =~] on o — — — — — — — [a¥] od

— —_— _—— — -— “» . - - . ’ * 29 — pu oO oN o © ° ~™ — o~ o S ~— aa ' 0 — ! o ' 1 — — ~ a. ~ oN o ~ wd -— o oo — 0 on oO oO x = } wy oy oy «y oy oy «y xs

O x x= x x x x= oN ot |=] |S} (SI LQ Oo oO oo r “ . > og x x3 x x =x = x ! + -r x = = = = = x ox Qo 0 Oo oO QO oO Oo oN o~ ‘ od oa o~ ~ . — — — —4 — . — —— 3 oy oy ~~ ~ oy © x x i x x = x xe oO QO Q wy © [&] [&] — ~~ —~— [& — ed —— [aa] £5 x x t x x= : x of |] O oO < QO |] [8] . . ; . 5

Lai] oN «Sy Lal hal © 3 oo x x x x x x x os ( O oo | 8) |] |S] [&] — . [= x x xi x x= x x ‘ od ~~ oS - — — x x x ore ° 2 Ort 5

QQ rt

La =x x “~ —_ «“ - 5 Sf o> x OQ [aa] hod 0 [aa] — — - — < © ta oO oO oO 0 o~ - - “- © ~ © x [aY] oN oy oN a , [a] oN s . ¢ * oO . ° ~~ -_ on ° 1 ~ « S a. ar — Ea © S Sg = 4 — o ~ ~ — ™ - ™ ~ m ~ o x x= x 5 3 5 = oS oO © © ht © ~ oy x " 5 oe oe x x = v ~ ~ = x = = - = = 35 8 5 3 oo Oo Oo © © © © o~ o o o > — -— — - Te yr

Pe) ~ mo = = = 5 3S 3

Oo [=1 'a) QQ hd © © = © = = = - x= x . 5 5 5 ox Oo 5} = © © © . pu. Pra} on oo La o ~ x x x 5S 3 5 o 5 5 wo . QO [&) ’ © 4 — =x ox = = = = = * - x ~

Q x oO o— ’ : : : ~ | / w — - Oo oO < © i © © 9 on o = = - = oo ~ - - - -

- a ———— ee ——— . - ~ eo t , 31 ° . = — - o — . a. } -— o «a ~ 2 a = o — — o — — } Co a) ™ a) Pa on Ia)

OO x x x x x =~ og Co QQ |S |] oO oO QQ “ , ~~ = . = . = = CQ = = = oe [&] oO [8] |S] QQ oO oN Nd o~ : —i — — 4 Lt — — [a la) — ™ ~~ : x : x x x os os . wy oO Qo « © haa) i oO = Se Q — | &) o\ 1 I x ¢ x 1 : of «= QQ QQ « : QO «= ~ [al oo al laa) oy oN x x= x = . x x ox J QQ QQ [8] QQ 0 . . } oz = x x x = x . . oe ' LN x . { 5S

Le Po ro . | : [6] - > C— — : oz - : oo . LQ — i ~4 - [3 o 2 “ 2 = © Co o - La o ~ ~~ — -

. ' 32 — bd [=]

Q \ wy QQ ° : oO — QQ ~~ — RN 1 RN ' «r — 1 QQ oN 1 Oo

Qs —~ oN «oy 0 «© x [=] = ~~ —4 ao 4 ~ L-] — ‘ oN oN o™ oN on ov oy

Oo x3 x = = x =x = [=] QQ Oo 9 |S) Q QQ |S] , i i ! [al a1 = x = x = = = oN x = -r = = oO = 1 = = xt QO oO QQ oo QQ QQ QQ od ~~ oN ~ — ————— — — ha la © ~ x x= x= =

Po } J x oO

Q ~ . ! — = = z : faa) = on : == = . — x ~ [= O) < Oo o — / . Q — od: [hal < Oy Oo ~ <5 <r Lod «r «r Es 4 r

. { - n ) 0 20 2 1 . 33 © ~ ° Q — o~N wv ~ o ” wv a. | 1 p) on wv ~ on — oo [2a] [2a] [aa “ ™ Lal

OO x= x x x= x x x ol . QO QQ oO 0 LQ |S) Q . «© of x= =~ =~ = x= x= x : i ar = = = = oo = = ox Q |S] oO © QQ oo oO o~ o~ o~ ~ oN o~ —_ — — — — — y [2a] oy [aal « oy x = x x = = & | 8] wy [&] OQ Qo Q — — x — — —~— — © xs x oN x x x = - ox oO QO Oo [8] 0 QQ [8] » wv . La) La) x o~ ~ [aa = oN x= x ~ x = = x [=] Q (8) |&) oo oO QQ Q — . . [= x p> 4 x x x x= =

Lo = O © © — oO wv} [5] > ha) ~~ ~ - = |S] [>] Ca. . ¢ oO oo an [en] ~~. oy ~ <r x -r <r oy wo “o « ow .

{ ; . i - 34 — oo ~ © o~ oo ° 7a) — = - — oN 1 ' © . t wy wy ' oa. oO oO oN Q o~ on ow — — Pe) = [hal Cm [aa] oy on oy oS © x x x x x x x x1 QO oO QO LQ QQ oO oO i 1 wr * [=] x = x x = rom x= ! «f = = = a = - = ' of |] QQ QO Q Q Oo . [&)] o~ . py . oN ~ [a] o~ oN x oN i la a) a) a) a) ~ o i x x x x x x x= [S] Q © oO QQ oo 0 oar — So — —— Nd — [al x x x x : x x x oF QO Q oO QQ Q Q QQ . ~ . : [1a] x . QQ [aa «Y oo oy [2a] ~™ ~~ 4 xo x x x x x . x 3 ox QO Q o |S) [ oO Oo . — [= x = = x x x x . ' —

S]

O, 0) <O = O © [3 > =() oS - x= : . NI o vy «> ~~ [>] [eal oO ~4 x 1 oN oN wy « a, 0 Oo t t — «© . o

QO oJ — ° <r —t —~ ST — on 1 1 1 «<r t~

Q. on ~N o = © — —

J. ™ lal la) Pa) 0 x= x x x x [=] oO QO Q o OO : wy . ox x x = x x or = = = . = a oO © Oo oO QS 1 “ oN x= x od [&] OQ oy : oN . ry ~ : = = x x o oN oy . oo QQ on OO [&)] . x

NN t == ' t oy OQ pe =4 - x QQ oN x x ~— oy [8] OQ nn x Qe OQ x on t t Oo ' QQ [2a] [a oN [al Lal oN x x = x x [= -] [8] © [&] (SJ |S} : — oe x x= = x . = 1

TO "0 + — 2 = 2 - — — x «< ow © 0 ov [aa] . «<r Fal £O x f Oo 0 Oo OO ©

: 26120 36 .

TABLE ITI

Compounds of formula :

R' fs

R 0 - (CH - CONH - - ( 273 ¢ R,

CN

No. Ry R R’ Mp. (°C) —— 1 CH(CH,), Cl CH, Oil 2 n-CcH, , Cl CH, Oil 3 CH(CH,), CH, Cl 4 n-CcH,, CH, Cl

I] .

Table IV

Compounds of formula

H . ¢ 3

H R

¢ 3 12

Cl O - CH - CO - NH - ¢ - Ry .

CN .

Oo. ° ' - N R, BR; Mp.(°C] 1 CH, n-C,H, 71-75 2 H C_H - } CH, He 86-87 3 C_H C_H 125-12 25 25 5-126 q H CH_CH(CH 01-10

C 3 2 ( 373 101-102 : S CH CH _OCH Oil 3 2 3 : - 6 H CH(CH,), 86-088 7 Cc CH_CH _CH(CH : 92-94

H, 2 2 ( 372 9 8 C_H CH _CH(CH_) 68-70 25 2 3°2 9 CH CH(CH_)C_H 103-109 3 3°25 . ) 10 CH(CH_ J, CH(CH 106-109 11 CH, ON 87-88 12 CH, -GH-CHy 127-129 . SCH, : 13 CH, CH, - 128-130 . 14 CH C(CH_) 110-115 ] 31°3 1 C_H 64-66 ~~ H JH

CH_CH _CH 66-70 16 H 3 ,CHy ] 7 H - 1 CH, Ce 5 148-152 18 CH CH_SC_H 78-82

J 2 2S oo 26120 38

Table V

Compounds of formula :

M3 Hs

Aryl - O - CH - CO - NH - C - R, '

CN

No. Aryl R, Mp.[(°C] 1 evss{O)- CH(CH,) , 83-86 : 2 CH(CHy), 74-76

CN

3 (Oy CH(CH,), | 71-75 ’ . F 0 q enooe{O)- CH(CH,), 110-115 “+o CH, 134-1137

Cl

NO. Aryl Ry Mp.[(°C]

EE

6 ct, {O)- CH(CH,), 80-82 7 0) CH(CH,), 74-76 . CH, 0) 8 C OO) CH(CH,), 134-136

C1 ro 9 ON CH(CH,), 101-105 \ (O CH(CH,), 94-99 3! 11 ar LON C(CH,) 4 126-130 cl ro

NO. Aryl R, Mp.[(°C} - 12 (0)- CH(CH,), 85-88

CH,

N

: 13 | (0) CH(CH,), 170-174

N

! . & 14 nC CH, 129-145 * Cl : x0 oo CH(CH,), 139-142 cl . 16 0,N oF _ CH(CH,), - 124-126

CH, .

CH

NO

» , + . 26120 41

NO . Aryl R, Mp.[°C] 18 ~O)-oresry CH(CH,), 78-80 19 CH, 0) CH(CH_), 87-92 ° . NO,

O,N ~o)- CH(CH,), 110-112 21 0) CH,SC_H, Oil : re - Cl . 22 “HOF from 112

CH, 23 ci/\ from 1}? \/

C1

No. Aryl R, Mp.[(°C]

CH

[ 24 CH(CH -

Cl

Table VI

Compounds of formula

NE Cats

Aryl - O - CH - CO - NH - c - C,He

CN

NO Acyl Mp(°C]

Cl 1 10) 100-102

N . 4 LO) 64-66 ’ CH, . S {O\- 92-93

CH, . Cl ! 6 OO} . BB-90

. ¢ : 44

No. Aryl 7 M(eC)

N

7 OF 84-87

Cl : N 8 cl ~O}- 129-131 y {0} 117-120 : Cl : 10 {0} 117-118

CH, . No, 11 {O)- 132-133 : CH, oo

No, 12 on {0} 120-122 . - 13 oO} 108-110 : 14 n-C,H,0 / ~ : 71-75%

— - . ® . ‘ 45 .

Table VII

Compounds of formula

HE M3

Aryl - O - CH - CO - NH - § - Ry

CONH

No. Aryl R, Mp.(°C]) 1 ‘Cl ~ - n-C,H, 100-102

CH, 2 Cl — )- n-C,H, 108-111

CH, 3 O\= n-C.H, 111-113

N

: cl

N

4 (O)- n-CJH, 115-117 cl

Table VIII

Compounds of formula

R R tl 12 .

Aryl - O - CH, - CO-N - C -R 2 ( 3 . CN

NO. i o

Aryl R, R, R, mMmp.[°C] -_—_—

H

C 3 1 oO) H CH, CH(CH,), 100-103

CH, 2 0{0)- H C,H, C,H, 86-88

CH, 0il : 3 c1-{( _ CH, C,H, CH(CH,) a c1{O)- H C,H C,H 50-52 - Oil “+O H CH, n-C.H i

CH

: i Co. 47 6

Table IX

Other compounds according to the invention 1 Cl O-CH_-CO-NH-C-CH(CH, ) 5

CONH,, Mp.105-107°C

H .

Cc 3

H

. § 3 THs CH, 2 Cl O-CH - CO -N - -CH(CH,), 0il

CN

¥ CH,

GHy HW 3 Cl (O} O-CH-CO-NH-C-C Hg Mp.61-63°C

CN. : Cl ; ° —_— CH, H 4 c1{ O)\-0-bu-co-nu-¢-n-c H Mp.70-74°C 37 jo WH

Cl

Claims

1. Fungicidal agents comprising of a compound of formula Acyl 1 2 ! yl = X - Q - CON - ¢ - Ry (1). Ry a wherein z 2 oi: i Aryl represents a phenyl group, either unsubstitu 4 - as or mono- to tri-substituted by C15 alkyl, | 2 8 23 TZ 3d Cig alkoxy, Cos alkyl-s0, (n= 0 or 2), halpgen, - 22 NO, , CFq, CN, CH30CH,, (CH3) NCH, , C00alkyl, 83 iE CONH, or phenyl; a 1- or 2-naphthyl group; an Co optionally chlorine-substituted 2-, 3- or 4-pyridyl group; a pyrimidyl or quinolyl group, 16 Re Q represents - C - (CH,) (m= 0, 1 or 2) Rg Ry represents H, C;_g alkyl, R, and Ry represent H, C6 alkyl (which may also contain an 0 or S atom in the chain), phenyl, C;_, . cycloalkyl, CH,-C00-(Cy_g alkyl), R, and Ry together may also represent =(CHy) y=» ~(CHy)g-» “eH— (CHy)4- CHy Ry represents CN, CONH,, Rg represents H, CHg, CoH Re represents H, CHy, ; X represents 0 or S, BAD ORIGINAL . ’ Rn emer : ;

optionally in the form of racemates or mixtures - of the optical isomers or in the form of the pure ’ ’ enantiomers or diastereomers, together with conventional excipients and/or carriers. j 5 2. Compounds of formula fk Aryl - X - Q - CON - C - Ry (1). Rg wherein Aryl represents a phenyl group, either unsubstituted : or mono- to tri-substituted by Cys alkyl, Cos alkoxy, Cq_g alkyl-s0, (n= 0 or 2), halogen, NO,, CFs, CN, CH,0CH,, (CH4),NCH,, CO0alkyl, CONH, or phenyl; a 1- or 2-naphthyl group; an optionally chlorine-substituted 2-, 3- or 4-pyridyl group; a pyrimidyl or quinolyl group, 6 Q represents - C - (CH), (m=0, 1or2) Rg Ry represents H, Cy-5 alkyl, R, and Ry represent H, C6 alkyl (which may also contain an 0 or S atom in the chain), C5_; cycloalkyl, CH,-C00-(C; _g alkyl), R, and Ry together may also represent ~(CHy) => -(CHy) gs eH —(CH,) 4- CH4 Ry represents CN, CONH, , p BAD ORIGINAL

(c) aryl-X-Q does not represent i j Cl cl (Gomes {Gomer Cl cl {Oy o-enteny CF 3 or : {O)-o-ente pi - ’

CF . : 1 if CRyR3R, represents C(CHq) uN; and (d) -X-Q-CONR;-CR RR, does not represent -0-CH, -CONH-CH, CN if aryl represents Pate O)y—- cl _ or : CONH,

3. Compounds as claimed in claim 2, wherein Ry is H, ( R, is CH, Ry is CH(CHy), and Ry is CN.

4. Compounds as claimed in claim 2, wherein aryl is z5 4-chlorophenyl, 4-chloro-2-methylphenyl, 2,4-, 3,4- or 3,5-dichlorophenyl.

5. Compounds as claimed in claim 2, wherein X represents 0. 1 i BAD ORIGINAL )

oo - 51 - Ce ————— Rg represents H, CHjs Cogs Rg represents H, CH, X represents 0 or S, optionally in the form of racemates Or mixtures of the optical jsomers or in the form of the pure enantiomers OY diastereomers, with the proviso that in formula 1 (a) aryl-X- does not represent CH : 3 4 if Q represents CH(CH,) and CRoR4R, represents -CHy CN and (b) aryl-X-Q does not represent

Cl cl if (1) R, represents H or Cia alkyl and (2) R, represents H, methyl or ethyl and { (3) Ry represents H, methyl, ethyl, phenyl, benzyl, R) and Ry together may 2150 represent (CHy)y or (CH) )g and (8) Ry represents CN; and , A s ' i LC 'D ORIGINAL 9d

6. Compounds 3S claimed in claim 2, wherein Q represents CH(CH,).

7. 2-(4-Chloro-2-methylphenoxy)-propionic acid- N-[2-cyano-3-methyibut-2-y1Jamide.

8. A method of combating phytopathogenic fungi which comprises treating plants subject to or subjected to fungal attack, seeds of such plants or the medium in which the plants are growing or are to be grown with a compound of Formula I as claimed in . claim 2.

g. A method as claimed in claim 8 in which the phytopathogenic : fungi are Piricularia and the plants are rice plants. INVENTORS: WOLFGANG BUCK ERICH RADDATZ \