PH27080A - New substituted alpha -pyrimidinyloxy (thio)-and alpha - triazinyloxy (thio) carboxylic acid derivatives - Google Patents

Description

2B % ®

Description 5

This invention relates to new substituted otpyri- & Cee, midinyloxy(thio)= and oktriazinyloxy(thio)carboxy- §

Ey lic acid derivatives, processes for their prepara- £ a 5 tion and their use as herbicides, fungicides and 2 plant growth regulators. i

It is known that pyrimidine derivatives possess her= £ bicidal activity (EP 223 406, 249 707, 249 708, 3 287 072, 287 079 and 347 Bll). However, the herbie Bg a cidal activity of these known compounds is often ine BR sufficient or selectivity problems are seen in ime # portant drops. M -

The object of the present invention is to make new compounds that do not have these disadvantages and 3 ~ have improved biological properties over the known i compounds. & -#

It has now been found that substituted of ~pyrimi- E dinyloxy(thio)= and ob-triazinyloxy(thio)carboxylio 5 ' acid derivatives of general formula I i 2 &

R A | &

EE | g

Va \N\__ x” ™ coor (1) ® : © Pm - - 2x oO 2 oo oP 7

Tr

—— b )

E in which 4 40

A is one of the groups A - 1 to A - 6 of general i : formula " oe :

R 4 6 b R J

R R 2 2 NF ~aF :

R be

YL RS i:

J 1 : 5 A= A-2 § : 6 RS RY 8

X

~~ 4 W

J A

- = ’ ‘ify .

A - 3 A - b #

I # ere R gf

Td or RY % tH i 8

A -5 A=b i on

LY a C.-C -alkyl or C.-C -cycloalkyl, both of which 5 . ' 1°76 3 6 hd ' are substituted by C,=Cy~alkoxy or halogen, & 2 straight-chain C,-Cg-alkenyl group, cyclopropyl or H : \ -3 w CG

E 1 a benzyl group, which is substituted on the aliphatic carbon atom by halogen or C=C" i Ce alkoxy or by methyl end C,=C~alkoxy or : halogen} £

D is oxygen, sulphur or the group “NRO =3 # rt is hydrogen, C,-C,~alkyl or benzyls &

R® and Rr, which may be the same or different, are ¢

C,-Cj~alkyl, C,-C, alkoxy, C,-C,-alkylthio, 1

C,-Cy=alkylamino, di=C,~C, ~alkylamino or ¥ halogen, with the proviso that when A is une & substituted phenyl, X is sulphur and Y ie 2 oo methine, 2 and Rr cannot both be methyl or one 3 i : cannot be methyl when the other is tert-bhtylg % : . rY, R, r, R’ and gS, which may be the same or dif & ) : 15 ferent, are hydrogen, C,=Cj~alkyl, C,=Cy~ale Y - koxy, amino, di-C, =C =alkylamino, nitro § df helogen, trifluoromethyl or phenylj n &

R’ is hydrogen or C,-C,~alkyls ) $

X is oxygen or sulphur, with the proviso that when &

X is not oxygen when A is allyl; and 3

Y is methine or nitrogen, with the proviso that Y 5 is not methine when A is l~chloroethyl or l= & methyl-2,2,2-trifluoroethyl} oo i as well as their alkali metal, alkaline earth metal i Pp snd organic ammonium salts, and their optical taomers GW

Ro -l- : & :

— ——————————— EE —————— ro . p ; show interesting herbicidal, fungicidal and plant 5 5, growth regulant activity. i ¥ "te,

The expression "halogen" means fluorine, chlorine, > bromine and iodine. By the term alkali metal is . meant lithium, sodium or potassium and by the term ‘ alkaline earth metal is meant calcium, strontium or barium. 2 i The compounds of the invention of general formula I 1 can be prepared for example . ok

A) by reacting a compound of general formula II #

RS 5 ’ / \ 10 (an 4 in which R°, RZ and Y have the meanings given ¥ under general formula I and rt is halogen, ® i alkylsulphonyl or phanylsulphonyl, with a 2 compound of general formula III ¥

A 5 ux” coor (rrr) in which A, rt and X have the meanings given & ¢ Ae : boro © 2

SLA : TEE Ce E g Joyo { 1 { under general formula I, in a suitable solvent in . the presence of a suitable base, or { Ce

B) by reacting a compound of general formula VIII

RZ . ham / ye (viii)

R3 > f in which RZ, rR, X and Y have the meanings given #& under general formula I, with a compound of g general formula IX - :

Fd 2 coor! (1x) ¥ in which A and R* have the meanings given under b

Iv 4 general formula I and Z is halogen or alkylsule i phonyloxy, in a suitable solvent in the pre=- § sence of a suitable base, or 5 & c) by reacting a compound of general formula X : ¥ 3 3 \

LL Bed ’ ~~ : { ™ coor* (x) ° CL

R : 1 2 3 { in which R°, Ry R”, X and Y have the meanings ; given under general formula I, with a compound A of general formula XI 3

A - RYO (XI) a 8

N

% in which Alhas the meanings given under general ¥ : 1 } formula I, with the exception of the groups A = i to A - 6, and © is halogen, alkylsulphonyloxy : : or phenylsulphonyloxy, in a suitable solvent in = the presence of a suitable base, 5 - and if desired (i) a compound of general formula I in i

A which rl is hydrogen, Cy=Cj=alkyl or benzyl, so ob- %

Fis ~ tained, is reacted with an alkali metal base or an = 5 alkaline earth metal base, in a suitable polar sole k iy vent, to give a compound of general formula I in 5 i which RY is an alkali metal atom or one equivalent ww of an alkaline earth metal atom, (ii) and/or if de- : sired, a compound of formula I in which mt is an al-~ io ” i GNA: kali metal atom or one equivalent of an alkaline x5 ghd oR earth metal atom, is reacted with a suitable acid v se

AE in a suitable solvent to give a compound of general E formula I in which R' is hydrogen, (iii) and/or if # - 7 - 1

! fo 0 7 & x desired, a compound of formula I in which g is : id hydrogen is reacted with a suitable base in a suit- * a able solvent to give a compound of general formula 3 tr

I in which rt is an alkali metal atom or one equi- ‘ valent of an alkaline earth metal atom or an ore : ganic ammonium groupe :

The individual process variants are preferably car- § ried out in the presence of a diluent. For this, { a solvent which is inert to the reactants is used. i %

Suitable solvents includes water, aliphatic, alie ® cyclic and aromatic hydrocarbons, that can be op=- 2 tionally chlorinated, such as for example hexane 1 cyclohexane, petroleum ether, ligroin, benzene, to= £ luene, xylene, methylene chloride, chloroform, car= 5 bon tetrachloride, ethylene chloride and trichloro= : cr ethane, ethers, such as for example diisopropyl i ether, dibutyl ether, propylene oxide, dioxane and § tetrahydrofuranj ketonea, such as for example ace= # tone, methyl ethyl ketone, methyl isopropyl ketone, 3 nitriles, such as for example acetonitrile and pro=- 4 pionitrile, alcohols, such as for example me thanol, & ethanol, isopropgnol, butanol and ethylene glycol, 8 esters, such as for example ethyl acetate and amyl ¥ acetates, amides, such as for examples dimethylforme £ % AD cre oot? : % d & 2 amide and dimethylacetamide, sulphones and sule . 44, phoxides, such as for example dimethyl sulphoxide, 4 Ce and bases, such as for example pyridine. v

The presence of a catalyst can be an advantage, ; 5 Suitable catalysts include potassium iodide and : onium compounds, such as quaternary ammonium, phos- phonium and arsonium compounds as well as sulphonium his compounds. Also suitable ara polyglycol ethers, A especially cyclic ethers, such as 18-crown~6, and &

Lid tertiary amines, such as for example tributylamine. 8

Preferred compounds are quaternary ammonium come 8 pounds, such as for example benzyltriethylammonium or chloride and tetrabutylammonium bromide, &

The reactions can be carried out under atmospheric a pressure but if desired higher or lower pressures 5 can be used. Bn

The process variant A) is preferably carried out in # an aromatic hydrocarbon, such as benzene, toluene # or xylene, a halogenated hydrocarbon, such as me« if b thylene chloride or chloroform, an alcohol, such as ps methanol, sthanol or isopropanol, in ether, such as for example diethyl ether, diisopropyl ether,’ x tetrahydrofuran or dioxane, a ketone, such as for & Pe example acetone or methyl ethyl ketone, &n ester, 4 (GN 5 oq OR pe . §

gy such as methyl acetate or ethyl acetate, or a polar : aprotic solvent, such as dimethyl formamide, dimethyl~ : Co acetamide or dimethyl sulphoxide, or another solvent, such as acetonitrile or water. : bi)

Bases that can be used include an alkali metal, such i as sodium or potassium, an alkali metal or alkaline § earth metal hydride, such as sodium hydride, — hydride or calcium hydride, a carbonate, such as so= ) t dium carbonate or potassium carbonate, or a metal & hydroxide, such as sodium hydroxide or potassium hy=- % droxide. ¥ : bi

The reaction is suitably carried out between room 3 temperature and the boiling point of the particular § solvent or solvent mixture. The reaction time lies i » between 1 and 24 hours, b . The reaction can also be carried out in the absence h of a solvent, at a temperature between 120 and 160°¢, i by using as alkali metal carbonate, such as anhye- i drous potassium carbonate. i] 3

Fhe preparation of the oehydroxy or of ~mercapto 3 carboxylic acid derivatives used in this process 3 variant can be carried out using the following lite~ i rature processes: J. Org. Chem. 33, 2565 (1968) Jo 4 a - ¥ 0 ons - 10 = ] _—

ee ——————————————————————— rr : 5 ad

AD oP 3

Amer. Chem. Soc. 95, 71k6 (1973); J. Chem. Soc. s 1957, 3262; J. Org. Chem. 33, 1831 (1968); Can. .

J. Chem. 60, (1982) 2707 and Bull. Soc. Chim. ;

Fr. 1969, 2721. 3

E

The process variants (i) and (ii) are preferably carried out in an alcohol, such as ethanol, propanol or isopropanol, a ketone, such as acetone or methyl i ethyl ketone, water or a mixture of water and a i polar solvent. %

Bh % ki

Bases that can be uaed include carbonates, such as 4 . sodium carbonate, potassium carbonate or calcium carbonate, and metal hydroxides, such as sodium hy~ # droxide or potassium hydroxide. } % i

The temperature of the reaction falls within room ; temperature and the boiling point of the particular ¥ o solvent or solvent mixture. The reaction time lies b 1 between 0,5 and 36 hours. i when converting an ester in which R is benzyl to bi the free acid a catalytic reduction (hydrogenation) 7 can also be used. “

Suitable solvents for process variant (iii) include L hydrocarbons, such as benzene, toluene or xylene, i halogenated hydrocarbons, such as methylene chlow i ride or chloroform, alcohols, such as methanol, i a i Peat

Ee - 11 = 3 Sore . 0”

ee ——————————————————— Ee A 5 oA oot ethanol or isopropanol, ethers, such as for exam~ : . ple diethyl ether, diisopropyl ether, tetrahydro= i furan or 1,4-dioxane,ketones, such as acetone or o methyl ethyl ketone, esters, such as methyl acetate i 5 or ethyl acetate, or nitriles, such as acetonitrile. .

Bases that can be used include an alkali metal, auch 5 as sodium or potassium, an alkali metal or alkaline 3 earth metal hydride, such as sodium hydride, potas- : gium hydride or calcium hydride, a carbonate, such ; as sodium carbonate, potassium carbonate or calcium 4 . carbonate, or a metal hydroxide, such as sodium hy- 1 droxide or potassium hydroxide. Organic ammonium 5 bases that can be used include for example, smmonia an slkylamine (primary amine), a dialkylamine g (secondary amine) or a trialkylamine (tertiary amine). i

The temperature of the reaction falls within room i temperature and the boiling point of the particular # solvent or solvent mixture. The reaction time lies between 5 minutes and 10 hours. i 3 guitable solvents for process variant B) include hye 1 drocarbons, such as benzene, toluene or xylene, halo- i genated hydrocarbons, such as methylene chloride 4 or chloroform, ethers, such as for example diethyl & ether, diisopropyl ether, tetrahydr. furan~or 1l,k= | LN (oP .12 - i

\ ; 7 : n ] 27080 '; ¥ dioxane, ketones, such as acetone or methyl ethyl ¥ ketone, esters, such as methyl acetate or ethyl i acetate, or polar aprotic solvents, such as dime- : thylformamide, dimethylacetamide or dimethyl sule i phoxide, and other solvents, such as acetonitrile ¥ or water, #

Bases that can be used include an alkali metal, such . as sodium or potassium, an alkali metal or alkaline 3 earth metal hydride, such as sodium hydride, potas- § sium hydride or calcium hydride, a carbonate, such £ as sodium carbonate, potassium carbonate, sodium 3 . hydrogen carbonate or potassium hydrogen carbonate, i or a metal hydroxide, such as sodium hydroxide or i : potassium hydroxide. 8

The temperature of the reaction falls within room w temperature and the boiling point of the particular 5 = solvent or solvent mixture. The reaction time lies § ; between 5 minutes and 24 hours. 4

The process variant C) is preferably carried out in g an aprotic solvent, such as benzene, toluene, Xy= i lene, tetrahydrofuran, diethyl ether, hexane, dime= & thyl formamide, dimethylacetamide or dimethyl sule 2 phoxide. For deprotinating the compound of general i formula X, a base, such as sodium hydride, potassium i] tert-butylate or lithium diisopropylamide can be : “A

Bp0 “13 - *

B oo i erm or x ; 7 i ‘yy used. A ° ee

The temperature of the reaction lies between «78 C. and the boiling point of the particular solvent or . 3 solvent mixture. The reaction time lies between i 5 0.5 and 24 hours. 3 %

Compounds of general formula X are described in the : literature or can be prepared by methods analogous 3 2 to those described in the literature. (Khim.~Farm, i a zh. 16 (8), 931-4 /19827; Ukr. Khim. Zh. (Russ. Ed) ° 49 (11), 1205-8 /19837; Fizol. Akt. Veshchestva 18. 3 75-9 /T9867; and USSR Patent 791746). x : fl

The compounds of the invention prepared by these ® processes can be isolated from the reaction mixtures o in conventional manner, for example by distillation 5 of the solvent at normal or reduced pressure, by : - precipitation with water or by extraction. &

A higher level of purity can be achieved as a rule %

By by column chromatography as well as by fractional & distillation or crystallisation. w

The compounds of the invention are, as a rule, % colourless and odourleass liquids or crystals that a

ES are soluble in water, slightly soluble in aliphtic # hydrocarbons such as petroleum ether, hexane, pen=~ 8 tane and cyclohexane and highly soluble in halo= 13 Ca i NA

Xo ore - 1h = Ww i :

Lob i

W i genated hydrocarbons, such as chloroform, methylene 3 chloride and carbon tetrachloride, aromatic hydro- * carbons, such as benzene, toluene and xylene, ethers, such as diethyl ether, tetrahydrofuran and ; dioxane, nitriles, such ss acetonitrile, alcohols, ; such as methanol and ethanol, amides, such as dime- : thyl formamide, and sulphoxides, such as dimethyl :

LY sulphoxide. f i

The compounds of the invention show a good herbi- i cidal activity in broad leaved weeds and grasses. § : A selective use in various crops is possible, for 3 example in such as rape, beets, soya beans, cotton, i : rice, barley, wheat and other cereals, Individual # active substances are particularly suitable as 2 selective herbicides in beet, cotton, soya and & cereals. However the compounds can be used for 4 control of weeds in permanent crops, such as for i example forestry, ornamental trees, fruit, vine, & citrus, nut, banana, coffee, tea, rubber, oil palm, £ cocoa, berry fruit and hop plantations and for the i selective control of weeds in annual crops. i

The compounds of the invention can used for example 4 against the following plant species:

Dicotyledonous weeds of the species Sinapis, Lepi= i do ; Core -15 - ps i ee ——————————————————————— i —— et eer i % - Hl %

Th hl

Es : dium, Galium, Stellaria, Matricaria, Anthenmis, B

Galinsoga, Chenopodium, Brassica, Urtica, Senecio, 2 oy

A

Amaranthus, Portulaca, Xanthium, Convolvuluas, Ipo= ; moea, Polygonum, Sesbania, Abrosia, Cirsium, Car- ' duus, Sonchus, Solanum, Rorippa, Lamium, Veronica, Ve

KS

Abutilon, Datura,Viola, Galeopsis, Papaver, Cen- # taurea and Chrysanthemum.

Monocotyledonous weeds of the species Avena, Alo- pecurus, Echinochloa, Setaria, Panicum, Digitaria, i 3

Poa, Eleusine, Brachiaria, Lolium, Bromus, Cyperus, 2

Agropyron, Sagittaria, Monocharia, Fimbristylis, 2

Eleocharis, Ischaemum and Apera. B® i &

The rates of use vary depending on the manner of pre- I postemergent use between 0.001 and 5S kg/ha. i

The compounds of the invention can also be used as i defoliants, desiccants and as total herbicides. £ af

They also influence plant growth and can thus be :

A used to influence plant growth of crops. Some come= » pounds also show fungicidal activity. n

The compounds of the invention can be ussd either i alone or in admixture with one another or with other active agents. Optionally, other plant-protective ® agents or pesticides can be added, depending on the & & i" i _—

A 0 © - 16 ~ BE & 0 i

L

: * 2 i purpose for the treatment. When it is desired to Vv broaden the spectrum of activity, other herbicides : fe can also be added. Herbicidally active mixing : partners suitable in this connection include for example, the active agents listed in Weed Abstracts, ; vol. 38, No. 3 (1989) under the heading "Liets of common names and abbreviations employed for current~ ly used herbicides and plant growth regulators in :

Weed Abstracta', % : 10 An improvement in the intensity and speed of action x} - can be obtained, for example, by addition of woe adjuvants, such as organic solvents, wetting agents »

Fi) and oils. Such additives may allow a decrease in : the dose. we

The designated ective ingredients or their mixtures £ oS } can suitably be used, for example, as powders, i & sf dusts, granules, solutions, emulsions or suspensions, with the addition of liquid and/or solid carriers 4 and/or diluents and, optionally, binding, wetting, 3 emulsifying and/or dispersing adjuvants. k

Suitable liquid carriers are, for example aliphatic & and aromatic hydrocarbons, such as benzene, toluene, § xylene, cyclohexanone, isophorone, dimethyl sul=- i i % 2 & - 1 (I Lo £ WAS {oo or

Coe i

A fi

- pee = bo . “4 : phoxide, dimethylformamide and other mineral=-oil ) fractions and plant oils. - “oo

Suitable solid carriers include mineral earths, e.g. bentonite, silica gel, talc, kaolin, attapule gite, limestone, silicic acid and plant products e.g. flours.

As surface-active agents there can be used for exam- A ple calcium lignosulphonate, polyoxyethylenealkyl=- ) phenyl ethers, naphthalenesulphonic acids and their ; salts, phenolsulphonic acids and their salts, form- :

B aldehyde condensates, fatty alcohol sulphates, as i - : well as substituted benzenesulphonic acids and their i salts. 3

The percentage of the active ingredient(s) in the : various preparations can vary within wide limits. ¥

For example, the compositions can contain about 10 ; to 90 percent by weight active ingredients, and about i 90 to 10 percent by weight liquid or solid carriers, : as well as, optionally up to 20 percent by weight of surfactant. :

The agents can be applied in customary fashion, for “ example with water as the carrier in spray mixture : volumes of approximately 100 to 1,000 1/ha. The : agents can be applied using low-volume or ultra-low= i eT

RC ah® oT -18 - oe ee —————————————————————————— meer oy »

Ls

Ww volume techniques or in the form of so-called ; microgrenules.

The preparation of these formulations can be care ried out in known manner, for example by milling or EY

S mixing processes. Optionally, individual components ) can be mixed just before use for example by the so- ) called commonly used tank-mixing method.

Formulations can be prepared, for example, from the : following ingredients. ; 1] 10 A) Wettable Powder 8 1) 25 percent by weight active ingredient & : 60 percent by weight kaolin A 10 percent by weight silicic acid 3 percent by weight of a mixture of calcium ¥ ix lignosulphonate and the sodium salt of N= 3 methyl=N~oleyltaurine d 2) 40 percent by weight active ingredient i 25 percent by weight bentonite & a5 25 percent by weight colloidal silicic acid ® 10 percent by weight of a mixture of calcium 4 lignosulphonate end alkylphenyl polyglycol ff ether x

B) Paste 4 45 percent by weight active ingredient % ach “19 = £r0 or

Te ¥ 4 b ee ————————————————— ee —, 0 0. .. i a & . percent by weight sodium aluminium silicate & 15 percent by weight cetyl polyglycol ether with “ 8 mol of ethylene oxide 5 # 2 percent by weight spindle oil 0 5 10 percent by weight polyethylene glycol “ 23% percent by weight water 3

C) Emulsifiable Concentrate & 25 percent by weight active ingredient Y = % 15 percent by weight cyclohexanone : 55 percent by weight xylene & } 5 percent by weight of a mixture of calcium % dodecylbenzenesulphonate and nonylphenol= 3 ;

Kd polyoxyethylene. 5

The following Examples illustrates the preparation ¥ nr of compounds of the Invention. ;

Example 1

Methyl 2-( 3-methoxyphenyl)=2-(4,6-dimethoxy=-2-pyrie= 3 ' 1 midinyloxy)acetate i 4 8 g (230 mmol) Methyl 2-(3-methoxyphenyl)glycolate i was dissolved in 100 ml dimethylformamide and treated i with 2.8 g (20.4 mmol) potassium carbonate. After 20 8 hi : minutes stirring, 8.8 g (40.7 mmol) 4,6-dimethoxy- ; 2-methylsulphinylpyrimidine was added and the mixture heated for 1 hour at 90°C. The reaction mixture was # i; "3 er 4s !

SH NAL an one - 20 = ANY

Wt a

Rr

. i € then poured into 100 ml water and extracted with . 100 ml ethyl acetate. The combined ethyl acetate H n i phase was washed with water, dried over magnesium : sulphate and evaporated. The residue was recrystal- 1ised from diisopropyl ether. :

Yield: 9.8 g = 73% of theory Y mp: 97-100°¢. 3

Example 2 is

TT 4 2-(l,6-dimethoxy-2-pyrimidinyloxy)-2-phenylacetic i

KE acid “ 5 g (16 mmol) Methyl 2-(4,6=dimethoxy=-2~pyrimidinyl= oxy)=-2-phenylacetate was dissolved in 50 ml water/ 4 : : ethanol (1:1) and treated with 0.9 g potassium hy=- 5 droxide. After stirring for 16 hours at room tem- = x perature, the mixture was extracted with ethyl amcete § ate. The aqueous phase was acidified with 10% hy=- 5

J drochloric acid until it was pH 2 and extracted with 3 ethyl acetate, After drying over magnesium sulphate, 8 the ethyl acetate phase was concentrated the solid “

We pe! residue recrystallised from diisopropyl ether/ethyl L i acetate mixture, )

Yield: 2.45 g = 51% of theory &

BY mp: 158-161°C B i ba oo a: og GW fo OF -2r - & oH

EB ee ————————————————————————— te & bp? #

Example 3 p

Methyl 2-(k ,6=dimethoxy-2-pyrimidinylthio)h=pentenonte .. 1.22 g (12.2 mmol) Diisopropylamine was dissolved in =~ ml tetrahydrofuran under nitrogen and treated > 5 with 7.8 ml (12.2 mmol) 1.6 M n-butyllithium in hexane’ at a temperature between -78 and -50°C. The mixture 2 was stirred for 20 minutes and then a solution of 3 B g (12.2 mmol) methyl 2-(h,6=-dimethoxy-2~pyrimidinyl- 4 thio)acetate in 30 ml tetrshydrofuran was added to the wr 10 reaction mixture and the mixture then atirred for 30 : minutes. 1.45 g (12.2 mmol) 3-Bromopropene was added, dropwise, to the solution. The reaction mixture was * slowly allowed to reach room temperature, with stirr- & ing, end then stirred for 20 hours. The mixture was 4 added to 100 ml ice/water and extracted with ethyl ¥ ts acetate. The ethyl acetate phase, after drying over i magnesium sulphate, was evaporated and then purified ba by medium presgure chromatography using hexane/ethyl 3 acetate as eluent. i

Yield: 0.9 g = 25.9% of theory & 220 : 1.5342 : p % 1

Preparation of the starting Material for Example i

Methyl 2-(lt,6-dimethoxy-2-pyrimidinylthio)acetate i 3 g (230 mmol) Methyl thioglycolate was dissolved in t i _— 4 0

Ea vO one - 22 - of # §

—— ee ———————————— mer g : : u t 3 250 ml dimethylformamide and treated with 16.3 g & & (115 mmol) potassium carbonate. After 20 minutes . stirring at room temperature, 50 g (2.3 mmol) 4,6~- y dimethoxy-2-methylsulphonylpyrimidine was added and ™ the mixture heated for 3 hours at 90°¢. The re- # action mixture was then poured into water and exe i tracted with ethyl acetate. The organic phase was } washed with water and dried over magnesium sulphate. 4

The solvent was distilled and the resulting crude i

A iw product was recrystallised from diisopropyl ether, i : Yield: U4h.6 g = 79.4% of theory i - mp: 67-69°C. ¢ a i

Example 4 i

Methyl 2-(l,6-dimethoxy-2-pyrimidinyloxy)~-3-fluoro=- i ¥ :

Z-methylbutanoate . i : 4 g (26.6 mmol) Methyl 3-fluoro-2-hydroxy=3-methyl- ir butanoate and 5.81 g (26.6 mmol) 4,6-dimethoxy-2=- g wu methylsulphonylpyrimidine were dissolved in 75 ml x dimethylformamide at 20°C. and treated with 1.84 ! g. (13.3 mmol) potassium carbonate. The suspension > was stirred for $ hours at 20°C. and heated for one f hour at 60°C. The reaction mixture was then poured 3 into 150 ml ice-water and extracted with three lots £ of 75 ml ethyl acetate. The combined ethyl acetate E a jt : phase was washed with water, dried over magne sium a ey

A ore 0 , » - 23- i 0 oo W ee —————————— EE —————————————— Ee ee rrr eer TT — ———— ' 9A0E ) # } sulnhnte, filtered and evaporated. The solid resi-~ } due wns purified by silica gel column chromatography using hexnane/ethyl acetate as eluent, :

Yield: 2.9 g = 37.7% of theory mp: 73=700C,

Bxample 5

Ret 2-(h,6=bimethoxy=2-pyrinidinyloxy)=3-fluore-3-methyl- ' butanoic acid RE 2 fg. (6.9 mmol) Methyl 2-(k,6-dimethoxy=2-pyrimidiny ld

Bi oxy)=~3=fluorc~3-methylbutanoate was dissolved in a 5 iu ¢ i mixture of 20 ml water and 10 ml methanol and treated # with 387 mg (6.9 mmol) potassium hydroxide. After 8 ) stirring tor 4 hours at 50°C. the mixture was added d 8 to 50 ml water and extracted with 50 ml ethyl acet- u bed . aH, ate. The aqueour phase was acidified with hydro=- io chloric acid until it was pH 2 and extracted with : three lots of 100 ml ethyl acetate. The combined i ethyl acetate phase was washed with water, dried 1 over magnesium sulphate, filtered and evaporated. "

Yield: 1.0 g = 54.5% of theory . mp. : 107-108°¢. A

In a similar manner, the following compounds of the / invention of general formula 1 were prepared: 3

RT ft GV ny ov pho - 2h - a i 3 i k 1 it ee ———————— A ———

EE ——————————— ie “ ~ | 3 50 : bx c,d 1 oA? : . | In a similar manner, the following compounds of the invention of gen £99)

I . 3 ; formula 1 were prepared: # i

Example A r! rR? rR? X Y Physical n

Sq oy ob —_Ne constant

Co : 3: ( ar

Co 4 CL ml 8 3-Pyridyl H OCH, OCH, 0 CH mp.: 191-183°¢C

Cl “ 7 2-(H-Methyl)-CH, OCH, DCH, 0 CH mp.: 148 148°C

I a

Co indolyl : £ i B Phenyl C{CH,), OCH OCH 0 CH mp.: 126-127°C i 33 3 3 o a 3 3-Methoxy- H OCH, OCH, 0 CH mp. : rer-1fioc phenyl ¥ . 3 t-Methoxy- CH, OCH, OCH, 0 CH mp. : g1-930c . phenyl CL

Lo at 11 t-Methoxy- H OCH, OCH, 0 CH mp. : 132-1730¢ no L phenyl # - 12 Phenyl cH, oCH, OCH, 0 CH mp.: BI-903¢F

Te. CH ' : 80- 8 13 Phenyl 3 OCH, OCH, 0 CH mp.: 80 Brat : - treme) ; 14 Phenyl H OCH, OCH, 0 CH mp.: 153-154°C - oh i tener

Phenyl CH, OCH, ocH n CH. mp: 05800 oo : 3 3 i eet §

A k 4

OL 16 Phenyl H OCH, OCH, .0 CH mp.: 148-143°¢ {R-Isomer) i ol 17 2-Thienyl CH, CH, OCH; OCH, 0 CH mp.: 87-889C al 3

Tuy oC - i . -

HL 18 2-Thienyl H OCH, OCH, 0 CH mp.: 136 Rk : 19 Phenyl CH,CH, OCH, OCH, 0 CH mp.: 82-84) 4-Fluoro- CH, OCH, OCH, 0 CH mp. : 02-95 } phenyl } ,

Co 21 4-Fluoro- H OCH, OCH, 0 CH mp.: 134-138%¢C phenyl i 22 3-Pyridyl CH, CH, OCH, OCH, 0 CH mp.: 65-679 : 23 Phenyl CH, SCH, SCH, 0 N mp. : ro oo 24 2,6-Di- CH, OCH, OCH, 0 CH mp. : o-oo RE

Co So fluorophenyl E : 0

Cd pd er 8 WA 4 AG

Fo) 0 . WE - 28 - 3 “7 B® i 1 2

Cl un i a ve | iH

RA = pe go x

ET ————— rn i 1 2 3 % :

SL Example A Rr R R X Y Physical i .

No. constant : oo 25 2,6-Di- H OCH OCH 0 CH mp. : 1a9-19¥ec

Te 3 3 by cae RBloraphenyd ! ¥

Cpe 26 t-Trifluoro-CH, OCH, OCH, 0 CH mp. : 117-1180¢ fe ce methylphenyl i

Lo 27 L-Trifluoro-H OCH, OCH, 0 CH mp. : 152-1550¢

C 1 methylphenyl ° n Ri 28 3-Thienyl CH, CH OCH, 0CH, 0 CH mp. : 94-959¢ 23 3-Thienyl H OCH, OCH, 0 CH mp.: 147-1489¢C ; (dec.) 4 4-Bromo- CH, OCH, OCH, 0 CH mp.: 104-1059¢ i phenyl i

A 31 4-Bromo- H oCH, OCH, 0 CH mp.: 168-1705C

Ph # , CT phenyl 5

TLL 32 3,5-Di- CH, OCH; OCH, 0 CH mp.: 125-12623¢C : . | fluorophenyl { ‘ 33 3,5-Di- H OCH, OCH, 0 CH mp.: 128-1313¢C ; i. : fluorophenyl \ i Po

To ‘ = - . ! ” '

C34 CH=CH, CH, OCH, OCH, 0 CH R, wrtue: nck : {in ethyl acetate) : : : H -value: 8 oo . 35 CH=CH, H OCH, OCH, 0 c R -Va 8 (in ethyl acetate) 36 Phenyl CH, OCH, NHCH, 0 N foam aN : mp.: > 59°C ! \ 37 Phenyl CH, CH, NHCH, 0 N mp.: 125-1308C .: 94-989GE 38 Phenyl CH, 0CH, NICH), 0 N mp 9 8 ’ ! 39 CH,-CH=CH, H OCH; OCH, S CH mp. : S190 ’ 40 Phenyl Benzyl OCH, OCH, 0 CH mp. : 123-120 40

A 2-Naphthyl CH, OCH, OCH, 0 CH mp. : 20g ) 42 2-Naphthyl H OCH, OCH, 0 CH mp: 170-171" ! 43 1-Naphthyl CH, OCH, OCH, 0 CH mp. : 126-1274 54 }-Naphthyl H OCH, OCH, 0 CH mp. : a ro X i . 45 Phenyl H CH_CH, CH,CH 0 CH mp.: 135-137;G : 23 23 o —

Co 4B Phenyl CH, OCH, OCH, S CH mp.: 984-95 oF GINA : pi 0 OR _.

Be —

BE

! ET , B® —~ it i ~ . 26 = 2 ee ——————————————— mm rr ree : wn » fi a

Example A rR! R? rR X Y Physical 2

Co C7 Phenyl H OCH, OCH, s CH mp. : 158-160°C; - 48 2-Thienyl CH, OCH, OCH, 0 CH mp. o-102° ot 49 CH=CH-CH, CH, OCH, OCH, 0 CH mp. : s0-61"c4 Ee 50 CH=CH-CH, H OCH, OCH, 0 CH mp. : 126-128°C, 51 2-Nitro- CH, OCH, OCH, 0 CH mp.: 103°¢ 3 phenyl 52 2-Nitro- MH oCH, OCH, 0 CH mp.: 162°C ks ; phenyl jo 53 2-Chloro- CH, OCH, OCH, 0 CH mp.: 118°C i phenyl 5 ’ | 54 2-Chloro- H ocH, OCH, 0 CH mp.: 180°C } | Ne phenyl & 3 55 Phenyl CH, OCH, CH, OCH CH, 0 CH mp.: 53-61°C 4 56 Phenyl H SCH, SCH, 0 CH JF 1,5745 2 : 57 Phenyl H OCH, CH, OCH, CHy 0 cH mp.: 158-160 G% : } 58 Cyclopropyl CH, OCH, OCH, 0 CH mp. ocd 59 Cyclopropyl H OCH, OCH, 0 CH oe. 147-148" : : f 60 CFICH,), CH CHy OCH, OCH 0 TH mp. 1-1 i - 61 CF (CH, I~ CH, CH, OCH, OCH, 0 CH mp.: 106 C i

Phenyl . i

B 62 ClCH) ,- CH, OCH, OCH, 0 CH mp. : 102-103°% (OCH) Cf i | a 63 CCLiCH,I, CH, OCH, OCH, 0 CH mp.: 109°C 8 54 ClCH.) ,- H OCH, OCH, 0 CH mp. 133-141.% : (ocH,) 0 § - 65 CFICH]), CH, CH, OCH; OCH, 0 N ng: 1.475 ® : 66 CCLICH,), CH CHy OCH, och, 0 CH mp.: 95-96 C § bo §7 ~~ 1-Fluoro- CH, OCH, OCH, 0 CH mp. : 99-100" Cf i cyclohexyl 2 , | 58 CF(CH I~ CH,CHy OCH; OCH, 0 N mp. : } Phenyl ®

Co 69 y-Methoxy- CHg OCH, OCH, 0 CH mp. 12-15°C§ cyclopentyl & i i ne : i po © — «27 = §° 3 : i ’ 8 ee ——— ee —— h oo 1 2 3 : i . . Example A R +R R X Y Physical i

Nee oo constant . 10 1-Methoxy- CH, OCH, OCH, 0 CH mp. : 128-130°C

RE : Co anpn)ehevyl . Ce oo i . ro mM CF(CH,)- H OCH OCH 0 CH mp.: 135-136.C - 3 3 3 . Phenyl i CL a 12 1-Fluoro- CH, OCH, OCH, 0 CH mp. : ro-sn’gl ! cyclopentyl oF xk ! 0 & ' - C . - Kl 13 CCH, CH) CH, OCH, 0CH, 0 CH mp.: 72-7¢ CG

Ho) (0 - (CH) LOCH, ) 3 ctoc - C C ot - i

T4 (OCH, CHy) CH, CH, 0 Hq 0CH, 0 H mp 71-72 ¥ (CH ) (Phenyl) k 1-Fluoro- H OCH, OCH, 0 CH mp.: 140-1415C

Co cyclohexyl , \. 16 CHF -Phenyl H OCH, OCH, 0 CH B

Lo i Wn - ae cl 117 CHF-Phenyl CH, CH, OCH, OCH, 0 CH 2 - 8 CHF-Phenyl H OCH, OCH, 0 N £ : ; lL 79 CHF-Phenyl CH, CH, OCH, OCH, 0 N ge . a i ] 80 CF(CHy)- H OCH, OCH, 0 N 2 L

Phenyl i. - ; B1 CLOCH, CH )- H OCH, OCH, 0 CH mp. 128-130C " (CH) (Phenyl) & 82 CLOCH, CH) - H OCH, OCH, .0 N » : (CH) (Phenyl) = . 5 ( 813 CLOCH, CH) CH, CH, OCH, OCH, Q N &

CN (CH,) (Phenyl) ES : 84 CCLICH,)- H OCH, 0CH, 0 CH B® i Phenyl } : 2 i 85 CCLICH,) CH, CH, OCH, OCH, Q * ; Phenyl » # 86 CCL(CH I~ H OCH, OCH, 0 N %

Phenyl i - CH cH 0 N gd ;o 87 CCLICH,) CH, CH, 0 3 0 3 5

HI . Phenyl ih

Co a

So 88 CHF -Phenyl H OCH, OCH, S CH 5

LK a : ig . Wh : 3 ad

AO Oo - 9 PE » : al “28 = &-

To E

Sin :

——————— A —— — A meet LLL LL EEE Eee ! Lo . % .

Lo 3 oe Example A rR rR? RJ X Y Physical ke

LL . . 3. oT NL |. LLL LS. : HF - “

B89 CHF-Phenyl CH, CH, OCH, OCH, S CH 5

Co 30 CHF-Phenyl H OCH OCH S N hi oo oo Lar 3 3 k ‘ Seg Te TRTEhReNy LC Li, Ly ULHy ulti os No ere >

CH) - : i; 92 CF (CH) H OCH, OCH, S CH CL

Phenyl if % . - C NY

Co 93 CF{CH,) CH, CHy OCH, OCH, S CH i . : Phenyl - ik ! 94 CECH I - H OCH, OCH, S N

Phenyl t

CF{CH)- CH, CH, OCH, OCH, S N & : | Phenyl ® : fh - | 36 1-FYrer H OCH, OCH, 0 CH mp.: 138-140 C { cvyrlopentyl i a 2

RE - - Lg, : : } 37 {-Fluoro CH, OCH, 0CH, 0 N 5 i oo cyclopentyl 2 1 - - CH kf 98 1-Fluoro H 0 3 OCH, 0 N o . cyclopentyl , ik Do 3 : 99 - t-Fluoro- CH, 0CH, OCH, 0 N i) J '

Co . ..ryrldohexyl : od 100 1-Fluoro- HM OCH, OCH 0 N 3 ; 3 3 Be

Fl cyclohexyl on : QCH 0 N R

LC 101 CFICH,), H OCH, 3 3

Sy - OCH OCH 0 CH mp.: 137-180 C i] 102 CUCH, CH) H CH, 3 p o : he (CH) (OCH) 2 ob ¥ . x i ( g } : : 1

L i r - 29 = A {

RIGINAL

EW, rt : & oe i oi Ne i cops ;

Ade Co i

BNE a Lm Se . Lo qf: 1 ee ————————— EF ———— meme 4

The following examples illustrates the possibilities : for use of the compounds of the invention. 5

Example A if

EE a

In a greenhoure, the noted plant species were treated 2 post-emergently with the noted compounds of the {nven= * tion, at a rate of 0.1 kg active ingredient/ha. The = compounds of the invention were sprayed evenly over 0 the plants as emulsions or suspensions in 500 litres i - water/ha. Two weeks after the treatment, the com- 4 pounds of the invention showed a high crop selectivity i in whent and maize with excellent activity against the Bf weeds. The comparison material did not show similar ui : high efficacy. 8 in the following table: : 0 = no damage i 1 = 1 - 24¥ damage : : 2 = 25 « 7h% damage i ¥ 3 = 75 - 89% damage H 4 = 90 - 100% damage { k :

HELAN = Helianthus annuus a %

ABUTH = Abutilon theophrasti ¥

GALAP = Galium aparine B

SEBEX = Secbania exaltata 3

SOLSS = Solanum spe i 3

VERTT: = Veronic persica 3 % v ge GW i oR - - 30 - i go

Fou fi f bi

Mi

154° ’ 27080 *

H.A G38 8 V pg

E B AE OE - Te

L VL BL R

Compound of the AT A E 5 P - 5 Invention N HP X Ss E

Example 12 1 33 3 3 3 :

Example 49 0 3 3 2 3 3

Example 50 1 3 3 3 3 3 ) - 5

Untreated oO 0 0 0 0 O : } 10 Comparison 3 : . oo Methyl 2-(4-imsopropyle 3 2 3 2 3 2 5 hemethyle5~oxoe2«imidae 3 o- 201in-2-yl)=l(5)=methyle i benzoate ¥ Ry

Example B ’ i

In a greenhouse, the noted plant species were treated } . — pre-emargently with the noted compounds of the ine 5 vention, at a rate of 1.0 kg active ingredient/ha. bs

The compounds of the invention were sprayed evenly bo over the soil as emulsions or suspensions in 500 § litres water/ha. Three weeks after the treatment, L it the compounds of the invention showed a high crop E selectivity in soysebeans, cotton, sunflowers, wheat ; and maize with excellent activity against the weeds. k 5

The comparison material did not show similar high i ’ -

Bg - ’ 2 bh AN - 3 > = 24 of\ . .

ee —————————————————————

E PP bo i # SI ] efficacy.

In the following table: VL 0 = no damage 1 = 1 = 2% damage : 5 2 = 25 = 7h» damage 3 = 75 - 89% damage 4 = 90 = 100% damage .

GLMXA = Glycine maxima ‘ - GOSHI = Gossypium hirsutum 4

HELAN = Helianthus annuus u 4 .

PRZAX = Triticum aestivum 8 7ZEAUX = Zea mays § si

PANSS = Panicum maximum :

GALAP = Galium aparine ¢

SOLAS = Solanum Sp. ’ 8

VERPE = Veronica persica i

Bh : i f ; 3 % { ¥ i 5 . 3 - Lr ono por

Bl or ® i ee ————————————————————— mr mmr = ov x

Ti iL

Co 6 6 HT Z P GS V

L, 0O ER E A A OE

X 8S L 2 A N L L R : sr

Compound of the M H A AMS ASP © 5S Invention A I N X X Ss P 8 E :

Example 12 1 01 0 1 3 3 4 3

Example 48 1 0 00 - - 33 4

Untreated oOo 0 0 0 0 00 0 O 4

Comparison ¥ : 10 Methyl 2-(h-isopropyl=t= 3 2 3 2 3 3 bh ho3 methyl-5-oxo=-2-imidazo- & : 1in-2-y1)=4(5)=methylben= & : zoate po: - &

Example C % #

In a greenhouse, he compound shown in the table was # : 3 applied at the rates given. For this the compounds * _ were applied in vessels containing 1500 ml water, t

The test plants there were treated at the 2 to 5 i jeaved stage. Three weeks after the treatment, the 2 damage to the plants was estimated. The compound fi of the invention showed strong activity againat im- 4 i portant rice weeds with good selectivity in paddy # 2 rice. 4

In the following Table: ¥

Q = no damare A Lr A

Wo. wl (GWA

Epp OF poh

B® “3% m i g

EEE ————— EE ———————————————eeeeeeeen : bi so %

A : . 1 = slight damage - 2 = medium damage 3 = heavy damage RS 4 = total destruction : ol

ORYSA = Oryza sativa &

ECHCG = Echinochloa crus~-galli .

SAGPY = saglttaria pygmeea §

SCPJU = Scirpus juncoides "

So MOOVA = Monochoria veginalis EY ] 10 ‘CYPSE = Cyperus serotinus

Compound of the water application 0 E 8 M C

Invention kg active ingredient/ R C A £ oY ha Yy H a g oO P _ Ag y UAE

Example 12 1.0 0 3 Ub # hob

Example D $

In a greenhouse, the noted plant species were treated 3 pre-emergently with the noted compounds of the in=- : vention, at a rate of 1.0 kg active ingredient/ha. a i

The compounds of the invention were sprayed evenly = = over the soil as emulsions Or suspensions in 500 % litres water/ha. Three weeks after the treatment, g i \ on WR - 34 - gv A

Tob LT

Fs ee ——— ’ , Cha IVEY aE , i . eT Co

H # Soh J L 2

Bd } aiid

E

- the compounds of the invention showed excellent v activity against the weeds. b

Eo er,

In the following table: &

He 0 = no damage 5 1 = 1 - 24% damage a 2 = 25 « 7h% damage 3 = 75 - 89% damage 4 4 = 90 - 100% damage ¥

AVEFA = Avena fatua 5

SETVI = Setaria viridis £

CYPES = Cyperus esculentus : y :

ABUTH = Abutilon theophrasti . 5: 5%

IPOSS = lpomoea purpurea .

MATCH = Matricaria chamomilla i Po

POLSS = Polygonum 8pe :

SOLSS = Solanum BP. ¥ &

VERPE = Veronica persica i

VIOsS = Viola 8p i . g j in i : iu ih

It -~ -35 = a wv or A 5 oP _

CC ——————————————————— eee os . abe ite 2 k &,

Aa 8 6 A 1 ¥ Bp 8 VV vV EY B P AO oOo F 1 go PU OTL L RO Ee

Compound of the F Vv ETS CS 8 P 5 -

Invention AI S HS HS SES =

Tove RE

Example 4 3 4 4 3 3 3 - = = - &

Example 5 3 4 4 3 3h o- = = =

Example 15 3 4 3 03 3 bb 3 3 kA H

Example 28 S53 3.33348 , ot — 10 Example 58 - 333 33 - = = = 4 : Example 59 - 4 3 3 3 5 = = = =

Untreated 6 00000000 0;

Example FE k #, x

In a greenhouse, the noted plant species were treated e ! 3 [- post-emergently with the noted compounds of the in- $ oo vention, at a rate of 0.1 kg factive ingredient/ha. i. 2 » The compounds of the invention were sprayed evenly 3 over the plants as emulsions in S00 litres water/hae. y -

Two weeks after the treatment, the compounds of the w invention showed a high crop gelectivity in cotton £ a with excellent activity against the weeds. The com=- ig : parison material did not show similar high efficacy. E:

In the following table: 1 . het 0 = no damage F- :

Cr : 1 = 1 - 24% damage 9 A xe - ? i : a

E oo ad] J - 36 - ® dl : = ee F a ——————————————————————— EE ———— rr . : “ N . go? ¥ a i : 2 = 25 = 74% damage S 3 = 75 - 89% ddmage : - 4 = 90 - 100% damage . i

GOSHI = Gossypium hirsutum 5

ALOMY = Alopecurus myosuroides :

PANGS = Panicum maximum

ABUTH = Abutilon theophrasti L

IPOS = Ipomea purpurea o : § = POLSG = Polygonum 8pe - 10 SOLSS = Solanum spe : oo VERPE = Veronica persica " Co : VIOSS = Viola ep E “ay a AP A I P 8 i Vv o L AB POO EFI " “s Oo NU OL L do 4

Compound of the H M 8S T S S 8 Pgs

Co. Invention 1 Y $s H 8 s Ss EgS

Nb .

Example U4 1 3 3 4 3 3 3 F - &E _ Untreated o oo 0 OOO of 0

Comparison / / 4 (EP O 3h7 811) - $

Compound No. 243 0 1.1 1 Or 1 2 150

Example IF

Le oy reenhouse. +»= noted plapt species were treated | < \

In ag | | “ cvot-emergently with the noted compounds of the inven- oC 5 op . Ld : Le - 37 - x

I 3 ee ———— term em err eerie ee —————————————————————— — w i ~ : % . of : - ~ ‘ N\ ; & - tion, at a rate of 0.1 kg active ingredient/hae 5

The compounds of the invention were sprayed evenly over the plants as emulsions in 500 litres water/ \ ha. Two weeks after the treatment, the compounds of tha invention showed a high crop selectivity in cotton with excellent activity against the weeds,

The comparison material did not show similar high “ efficacy. o In the following table: " - 10 0 = no damage § ’ 1 = 1 « 24% damage Co 2 = 25 = 74% damage A : 3 = 75 = 89% damage L ; 4 = 90 - 1005 damage 2

QOSHI = Gossypium hirsutum ’ ¥

AGRRE = Elymus repens 4

Co! Pi : }

BROT = Bromus tectorum ;

SETVI = Setaria viridis { : PANSS = Panicum maximum / ;

SORHA = Sorghum halepense . ’ iF to

ABUTH = Abutilon theophrasti J

GALAP = Galium aparine / ; i

IPOSS = Ipomea purpurea if LE

MATCH = M~+ “v7ria chamomilla SE \ - POLSS = Polygonum sp. y \ } 5 LATE ge ) » A Be , v - 38 « Fa iwc - . ~ i Se

A a

Co ————— eer eer eee eee —— —— i h fe , i oo SEBEX = Sesbania exaltata i}

VERPE = Veronica persica i

G ABS PS AGI NI SV

0 G REA OBATPAMNDO EE s R OT N RUL OTL B R

Componnd of the H ET UV S HTAS C8 EP

Invention I E EI 8 AH P S H B X E

Example 5 1333333333843 oe Untreated 0 0000 OOO OO 3 0 0 - 10 Comparison }

Cy ’ (EP O 347 811)

Compound lo. 4 01 0 2 2 2 02 003 2 2 i 7 & . / ? / hid

IE (GNA - 39 - t BAD oF

Claims (1)

1. ee ————————————— Pa —

   A . QO 4 - CLAIMS: k

   ¢ l. Substituted q-pyrimidinyloxy(thio)= and q- # triazinyloxy(thio)=-carboxylic acid derivatives of § % general formula I 2 2 ¥ > X A ; ~ 5 \ ; »/ i in which 8 rL is hydrogen, C=C, ~alkyl or benzyl; 5 r® and Rr, which may be the same of different, are . . i - C,=Cy-alkyl, €,~C-alkoxy, C,-C,~alkylthio, § with the proviso that when A is unsubstituted : phenyl, X is sulphur and Y is methine, R® and s R’ cannot both be methyl or one cannot be = methyl when the other is tert.-butylj xX A is one of the groups A-l1 to A=5 of general formula : rE ’t y J g

   \. 4 i ’ : X 27 SN § rN Ler g gS BAD OR A 1 ¢ — % % - B40 - 3 a ———— — ee meee © _— ee ——————————— eee i i Co in which ¥ rY, Rr, RS, R’ and gS, which may be the same or : - different, are hydrogen, C,._y~-8lkoxy, nitro, halogen - or trifluoromethyl} r A - 2 is pyridyl, § 7 A - 3 is naphthyl, i : A - 4 is thienyl and 5 \ ¢ RY IN N 4 i As b o

   ¥ a. in which ] } 4 ¥ R' is hydrogen or N-methyl, 2 Co X is oxygen or sulphur, with the proviso that when y : X is not oxygen when A is allyl; and £ Y is methine or nitrogen, with the proviso that ¥ 5 ’ is not methine when A is l-chloroethyl or l= pr . 15 methyl-2,2,2-trifluorethyl; as well as their al- ; : kali metal, alkaline earth metal and orang fe- 8 monium salts, and their optical isomers. ” v i AL x GN ! o } ahd oR - & - 841 - : i

   Ce ————————— rm Sg op pi SE i so ’ D 507080 § } : 7 po 2 Ahherbicidal composition which comprises a & compound according to Claim 1, in admixture with 5 Ce agriculturally acceptable carriers or diluents. 3

   Co . | Je A method of combating weeds which comprises 3 ] Lo 5 applying to the weeds or their locus a compound 3 according to Claim 1 at the rate 0.0001 to 5 kg/ha. , *

   j . & 4 Sy .

   DR. CHRISTOPH HARDE - br

   DR. ERHARD NORDHOFF b

   DR. ANITA KRUGER : 2 Cy : DR. GABRIELLE KRUGER 25 Po

   DR. GERHARD TARARA ‘ ’ : DR. PETER WEGNER : - - 4 : i DR. NIKOLAUS HEINRICH 8 a ; DR. CLEMENS KOTTER 9 .

   DR. GERHARD JOHANN - -

   DR. RICHARD REES 3 . : : Inventors 3 . i be . . ol . : 3 Co : 2 : Co ¥ Lo Na 3 ! : a i

   SL . A , i" oN = h2 = Le k-.7 ” a cy - \ » 4 Saag TTT RB