IL95937A - Heterocyclic compounds, their manufacture and their use as herbicides and plant growth regulants - Google Patents

Description

95937/2 Heterocyclic compounds, their manufacture and their use as herbicides and plant growth regulants CIBA-GEIGY A.G .81765 Ref. 6102/73 The present invention is concerned with heterocyclic compounds, namely 2-heterocyclyloxy/thio-pyr imidines and -1, 3 , 5-triazines of the general formula wherein W signifies one of the divalent groups 11 12 R R I d) - C C - 1 2 . .

X. Y and Y each signify oxygen or sulphur, . . 13 Z signifies CR or nitrogen.

Pa/25.9.90 signifies hydrogen, fluorine, chlorine. C.^ - -alkyl, halomethyl, methoxymethyl . C 3~alkoxy, dif luororaethoxy or methylthio. signifies methyl, 2~alkoxy, C-^-fluoro- alkoxy, 2-alkylamino , diCC.^ 2~alkyl ) amino or N-methoxymethylamino , signifies hydrogen, fluorine, chlorine, bromine, optionally substituted C, ,-alkyl, C_ ,-alkenyl, C2 3~alkY'I1y'1 ' optionally substituted phenyl, hydroxy, optionally substituted C. .-alkoxy, 1—6 C. -alkylthio. phenoxy. phenylthio. cyano. 1—6 rhodano, formyl, carboxy, c -alkoxycarbonyl , 2—5 carbamoyl, formyloxy, C -alkanoyloxy , C - 2—5 2-5 -alkoxycarbonyloxy, 3-alkylcarbamoyloxy . di(C 2~alkyl ) carbamoyloxy or di(C 2~alkoxy)- phosphonyl , signifies hydrogen, 6-alkyl or trif luoromethyl. signifies hydrogen, C. ,-alkyl or optionally 1—0 substituted phenyl, signifies hydrogen or methyl, 8 9 and R each independently signify hydrogen or C1_3-alkyl, signifies hydrogen or C -alkoxy, 12 . . . and R each independently signify hydrogen or C -alkyl. 13 R signifies hydrogen, fluorine, chlorine or methyl a d 14 R signifies hydrogen, halogen, C1_2~alkyl or 2~alkoxy.

Israel Patent No. 55459 describes herbicidally active compounds of the formula (A), wherein X is oxygen, A, B and D are inter alia hydrogen, halogen, Ci-Cs-alkylthio , Ci-Ce-haloalkyl , Ci-Cfe-alkoxyalkyl optionally substituted with halogen, Ci-Cg-alkylamio or C-C6-dialkylamino, R2, R3, R¾, R5 and R6 are Inter alia methyl-enedioxy and ethylenedioxy wherein two adjacent carbon atoms of the phenyl ring are bridged.

The compounds in accordance with the invention, namely the compounds of formula I, have herbicidal activity and are suitable as active ingredients of weed control compositions. Furthermore, the compounds in accordance with the invention have plant growth regulating activity; they are thus suitable, inter alia, as agents for - 3 - positively influencing the growth of crops. Accordingly, the invention also embraces weed control compositions and plant growth regulating compositions which contain compounds in accordance with the invention as active ingredients, a process for the manufacture of these compounds as well as the use of the compounds or compositions for the control of weeds or for the regulation of plant growth.

In formula I above "halogen" as such or as part of a more complex group, e.g. halomethyl, embraces fluorine, chlorine, bromine and iodine, with fluorine and chlorine generally being preferred. The alkyl, alkenyl and alkynyl residues can be straight-chain or branched, and this also applies to the or each alkyl part of the alkoxy, alkyl-thio. alkoxycar bonyl and other alkyl-containing groups. The preferred 3~alkenyl and -alkynyl groups are vinyl and, respectively, ethynyl. A halomethyl or fluoroalkoxy group can have one or more halogen or fluorine atoms, respectively, with chloromethyl , tr if luoromethyl and dif luoromethoxy being examples of such groups. Optionally 3 substituted C. , -alkyl (R ) is especially an alkyl 1— b group which can be substituted with halogen (especially chlorine), hydroxy, methoxy, ethoxy, nitro, cyano, vinyl. ethynyl, carboxy, C_ -alkoxycarbonyl (especially ώ — b methoxy- or ethoxycar bonyl ) or a phenyl group which is optionally substituted (especially with methoxy). The preferred optionally substituted alkyl group is optionally substituted methyl or ethyl, especially the former group. 3 Optionally substituted C, „-alkoxy (R ) is especially 1—6 an alkoxy group which can be substituted with halogen (especially fluorine or chlorine), vinyl, ethynyl, cyclo-propyl, phenyl. C1_2-alkoxy, C1_2~alkylthio . cyano. carboxy. C -alkoxycarbonyl (especially methoxy- or 2 — 5 ethoxycar bonyl ) , carbamoyl, -iC^ 2~alkyl ) car bamoyl , N,N-di(C -alkyl ) carbamoyl or C -alkylideneimino- - 4 - oxy. An optionally substituted phenyl group (R . R ) can have as substituents especially fluorine, chlorine, methyl, methoxy or tr if luoromethyl . The preferred C_ _- 2—5 -alkanoyloxy, C -alkoxycar bonyloxy , C_ -alkyl- 2—5 2—3 carbamoyloxy, di(C -alkyl ) carbamoyloxy and di(C - 3 ~™ -alkoxy ) phosphonyl groups (R ) are acetyloxy or propionyloxy; methoxycar bonyloxy or ethoxycar bonyloxy ; methylcarbamoyloxy ; dimethylcar bamoyloxy ; or dimethoxy-phosphonyl .

When an asymmetric carbon atom is present in the compounds of formula I. the compounds can occur in optically isomeric forms. Geometric isomerism can also occur when an aliphatic C=C double bond is present.

Formula I is intended to embrace these and any other isomeric forms as well as mixtures thereof.

A particular group of compounds of formula I comprises . . 3 those in which W signifies a group a), wherein R signifies hydrogen, fluorine, chlorine, bromine, optionally substituted C. , -alkyl (in which a L — o substituent which may be present is especially halogen, methoxy, ethoxy, nitro, cyano, methoxycar bonyl . ethoxy-carbonyl, phenyl or methoxyphenyl ) , C2_3-alkenyl , C2 -alkynyl, optionally substituted phenyl (in which a substituent which may be present is especially fluorine, chlorine, methyl, methoxy or trif luoromethyl) , hydroxy, C_ -alkoxy, C, -alkylthio, phenoxy, phenylthio, 1— b 1— D 4 cyano or C_ c-alkoxycarbonyl and R signifies hydrogen 3 or C. .-alkyl, or R signifies hydrogen, fluorine, 1 — D chlorine, bromine, C -alkyl, hydroxy, C .-alkoxy, 1- 6 1- 6 .

C1_6-alkylthio . phenoxy, phenylthio or cyano and R signifies trif luormethyl; or W signifies a group b), c) or 5 12 . . . d) in which R -R have the significances given above; 1 2 and X signifies oxygen, Y and Y each signify oxygen . . 13 . 1 . . . or sulphur, Z signifies CR or nitrogen, R signifies - 5 - fluorine, chlorine, C -alkyl. f luoromethyl , methoxy- 7 2 methyl, C-^-alkoxy. dif luoromethoxy or methylthio, R signifies methyl, C -alkoxy or C -f luoroalkoxy. 13 . .

R signifies hydrogen, fluorine, chlorine or methyl and 14 R signifies hydrogen.

Independently of each other. W preferably signifies a group a) or b), especially a group a); X and/or Y1, but especially both X and Y1, preferably signify oxygen; 2 . . .

Y preferably signifies oxygen; Z preferably signifies CH or nitrogen, especially CH; R1 preferably signifies hydrogen, chlorine, methyl, methoxy or dif luoromethoxy and 2 R preferably signifies methoxy, ethoxy, methylamino, dimethylamino or N-methoxymethylamino . with the combination R1 and R2 in which at least one methoxy 3 group is present being especially preferred; R of group a) preferably signifies hydrogen, vinyl, ethynyl, hydroxy, C1_4-alkoxy , C1 2-alkoxy substituted with halogen, vinyl, ethynyl, C 2~alkoxy. cyano, carboxy or c -alkoxycarbonyl . C -alkylthio. cyano, car boxymethyl , C -alkoxycar bonyl-methyl or carbamoyl 4 . and R preferably signifies hydrogen or C -alkyl; 5 . . .

R of group b) preferably signifies hydrogen or 6 . . . 7 C -alkyl and R preferably signifies hydrogen; R , 8 9 R and R of group c) each preferably signify hydrogen 11 12 or methyl; R and R of group d) each preferably 14 methyl; and R preferably signifies especially "hTyd'rogen Especially preferred individual compounds of formula I are : 7-[ (4, 6-Dimethoxy-py imidin-2-yl)oxy]-3-methyl- -phtha 1 ide . 7- [ ( 4 , 6-dimethoxy-pyr imidin-2-yl ) oxy] -phthai ide , 3-ethyl-7-[(4.6-dimethoxy-pyr imidin-2-yl ) oxy] -phthai ide , - 6 - 7- [ (4 , 6-dime hoxy-pyr imid in- 2 -yl ) oxy ]-3-isopropyl--phthalide , 7- [ ( , 6-dimethoxy-pyr imid in- 2 -yl ) ox ] -3-methoxy--phthalide , 7-[ (4-methoxy-6-methyl-pyrimidin-2-yl)oxy]-3-methyl- -phthalide, 7- [ ( .6-dime hoxy-l .3.5-triazin-2-yl) oxy ] - 3 -me thy1--phthalide , 3-ethylidene-7-[ (4, 6-dimethoxy-pyrimidin-2-yl)oxy]--phthalide (especially its (Z)-isomer). 8- [ (4, 6-dimethoxy-pyrimidin-2-yl)oxy]-3-methyl--isochroman-l-one. 7- [ (4 , 6-dimethoxy-pyr imid in-2 -yl ) thio] -3-methy1--phthalide, 3-ethoxy-7- [ ( .6-dimethoxy-pyr imid in- 2-yl ) oxy ] - -phthalide , 7- [ ( 4 , 6-dimethoxy-pyr imid in-2 -yl )oxy]-3.6-dimethyl--phthalide , 7- [ (4 , 6-dimethoxy-pyr imid in- 2-yl ) oxy ] -3-methoxy-3--methyl-phthalide , 3 -carbamoyl -7- [ (4.6-dimethoxy-pyr imid in- 2-yl ) oxy] --phthalide, 3-(2-chloroethoxy)-7-[(4, 6-d imethoxy-pyr imid in-2-yl ) -oxy]phthalide, 7- [ ( 4 , 6-d imethoxy-pyr imid in- 2-yl) ox ] -3-pr opa g loxy- -phtha 1 ide , 7- [ ( 4.6-dimethoxy-pyr imidi n-2-yl)oxy]-3-(n-propoxy)--phthalide, 7- [ ( 4.6-dimethoxy-pyr imid in-2-yl) oxy] -3- ( 2-methoxy-ethoxy) -phthalide, 7- [ (4-chlor-6-methoxy-pyr imidin-2-yl) oxy ] -3 -me thy1--phthalide, 7- [ ( 4-methoxy-pyr imidin-2-yl ) oxy ]- 3-me thyl-phtha 1 ide, 7- [ ( -ethoxy-6-methoxy-pyr imidi n-2-yl) oxy] -3-me hy1--phthalide, 7- [ ( 4-chloro-6-methoxy-pyr imid in-2-yl) oxy ] -3-me hoxy--phtha 1 ide , 7- [ ( .6-dime hoxy-l .3,5-triazin-2-yl)thio ] -3 -methy1--phthalide, 7-[ (4-dimethylamino-6-methoxy-l, 3.5-triazin-2-yl)oxy]--3-methyl-pht al ide . 7- [ ( 4-methoxy-6-meth l-l .3.5-triazin-2-yl) oxy ] -3--methyl-phthalide , 7-[ ( -methoxy-6-meth lamino-l , 3,5-triazin-2-yl)oxy]-3--methyl-phthal ide , 7- [(4-chloro-6-methylamino-1.3.5-triazin-2-yl)oxy]-3--methyl-phthalide , 3-ethyl-7-[(4, 6-dimethoxy-l .3.5-triazin-2-yl)oxy]--phthalide . 8- [ (4 , 6-dimethoxy-pyr imidin-2-yl)oxy]-3,4-dimethyl--isochroman-2-one , 7-[ (4.6-dime hoxy-pyr imidin-2-yl) oxy] -3 -hydroxy--phthalide , 7- [ ( 4.6-dimethoxy-pyr imidin-2-yl )oxy]-3-methylthio--phthalide , 7-[ (4, 6-dimethoxy-pyr imidin-2-yl ) oxy] -3-vinyl--phthalide . 3-cyano-7- [ ( , 6-dimethoxy-pyr imidin-2-yl)oxy]--phthalide. 3-cyanomethoxy-7- [ ( .6-dimethoxy-pyr imidin-2-yl)oxy]--phthalide , 7- [ (4, 6-dimethoxy-pyr imid in-2-yl ) oxy ] -3- (methoxy-car bonylmethoxy) -phthalide, 3-ethoxycar bonylme thy1-7- [ ( , 6-dimethoxy-pyr imid in-2--yl)oxy]-phthalide, 7- [ (4 , 6-dimethoxy-pyr imid in-2-yl )oxy]-3-methyl-2-benzo-thiophen-1 ( 3H) -one , 7- [ (4 , 6-dimethoxy-pyr imid in- 2 -yl ) oxy ] -3-methyl--isobenzofuran-l(3H)-thione, 7-[ (4.6-dimethoxy-l, 3 , 5- tr iaz in-2-yl ) oxy] -3-methyl--isobenzofuran-l(3H)-thione. 7- [ (4-dif luo omethoxy-6-methoxy-pyr imidin-2-yl ) oxy ] -3-methyl-phthal ide , - 8 - 8- [ ( , 6-dimethoxy-pyr imid in-2-yl ) oxy] -4-methy1-isochroman-l-one and 3-acetoxy-7- [ (4 , 6-dimethoxy-pyr imid in-2-yl ) oxy ]-phthalide .

Further representatives of compounds of formula I are: 7- [ ( .6-Dimethoxy-pyr imidin-2-yl)oxy]-3-isobutyl--phthalide , 7-[ (4, 6-dimethoxy-py imidin-2-yl) oxy] -3 -sec. butyl--phthalide. those compounds of formula I in which W signifies a 1 2 . . . . group a), X, Y and Y all signify oxygen. Z signifies 1 2 4 14 CH, R and R both signify methoxy. R and R 3 . . . ·= : ~ both signify hydrogen and R signifies bromine, chloro-methyl, t ichloromethyl . hydr oxymethyl , methoxymethyl , cyanomethyl. "car boxymethyl . methoxycar bonylmethyl . allyl. ethynyl. propargyl. n-butoxy, cyclopropylmethoxy , dif luoromethoxy . 2 , 2 , 2- tr if luoroethoxy . methoxymethoxy , methylthiomethoxy . 2-methylthio-ethoxy . car boxymethoxy . 1-car boxyethoxy . 1-methoxycar bonyl-ethoxy , ethoxycar bonyl-methoxy. 1-ethoxycar bonyl-ethoxy . N-methylca bamoyl-methoxy, 2- (N. -dimethylamino ) -ethoxy , formyl. carboxy, ethoxycar bonyl . formyloxy, acetyloxy. methoxycar bonyloxy . ethoxycar bonyloxy or N.N-dimethylcarbamoyloxy; those compounds of formula I in which W signifies a 1 2 . . . . . group a). X. Y and Y all signify oxygen, Z signifies 1 2 . . 4 . . .

CH, R and R both signify methoxy, R signifies 14 . . . 3 . . . methyl, R . signifies hydrogen and R signifies fluorine, vinyl, hydroxy, ethoxy. methylthio. carboxy or methoxycar bonyl ; 3-ethyl-7-[(4, 6-dimethyl-pyrimidin-2-yl)oxy]-3-methoxy--phthalide , 7- [ ( 4 , 6-dimethyl-pyr imid in-2-yl ) oxy] -3 -methoxy- 3- t i-f luoromethyl-phthalide. 3-ethoxy-7- [ ( 4.6-dimethyl-pyr imidin-2-yl)oxy]-3-tri-f luoromethyl-phthal ide . - 9 - those compounds of formula I in which W signifies a those compounds of formula I in which W signifies a 1 2 group a). X. Y and Y all signify oxygen. Z signifies 2 3 4 CH, R signifies methoxy. R signifies methyl. R 14 . 1 and R both signify hydrogen and R signifies fluorine, ethyl or methylthio; those compounds of formula I in which W signifies a 1 2 . . group a), X, Y and Y all signify oxygen, Z signifies 1 - 3 4 CH, R signifies methoxy, R signifies methyl, R 14 2 and R both signify hydrogen and R signifies methyl- ami those compounds of formula I in which W signifies a 1 3 . . group a), X, Y and Y all signify oxygen, Z signifies 1 2 . . 4 nitrogen, R and R both signify methoxy, R and 14 3 R both signify hydrogen and R signifies hydrogen. ethyl, n-propyl or n-butyl; 7-[ (4-methoxy-6-{N-methoxymethylamino} -1.3, 5- - tr iazin-2-yl ) oxy] -3-methyl-phthalide, 7- [ ( 4 , 6-dime hoxy-1 , 3,5-triazin-2-yl) oxy ] - 3 -methoxy- 3 - -methyl-phthalide, 7-[ (4.6-dimethyl-l.3.5- tr iaz in-2-yl ) oxy ] -3 -methy1- -phthalide. those compounds of formula I in which W signifies a 1 2 group a), X, Y and Y all signify oxygen, Z signifies 1 2 3 CH, R and R both signify dif luoromethoxy , R . . 4 signifies hydrogen, methoxy or ethoxy, R signifies 14 hydrogen, methyl or ethyl and R signifies hydrogen; Λ - 10 - thos ifies a . group a) fies sulphur. methoxy, signifie . hydroxy, methoxy, ethoxy or methoxycar bonylox ; 7- [ (4 , 6-dimethoxy-pyr imidin-2-yl ) thio] -3-me thy1--isobenzofuran-l(3H)-thione. 7- [ ( 4.6-dimethoxy-pyr imid in- 2 -yl ) thio] -3-me thy1-2- -benzothiophen-1 ( 3H) -one , 7- [ (4.6-dimethoxy-pyr imid in-2 -yl ) ox ] -3-methyl-2-benzo-thiophen-l(3H)-thione, 3-ethyl-7-[(4, 6-dimethoxy-pyr imid in-2-yl ) ox ] - isobenzo-furan-1 ( 3H) - thione , 7- [ (4 , 6-dimethoxy-py imid in-2 -yl ) oxy ] -3-me thoxy--isobenzofuran-l(3H) -thione, 3-ethyl-7-[(4, 6-dimethoxy-pyr imid in-2-yl ) oxy ] -2-benzo-thiophen-l(3H)-one, 7-[ (4.6-dimethoxy-pyrimidin-2-yl)oxy]-3-methoxy-2- -benzothiophen-1 ( 3H) -one . 7- [ (4 , 6-dimethyl-pyr imidin-2-yl ) thio] -3-me th 1--phthalide , 7- [ (4-methoxy-6-methyl-pyr imidin-2-yl)thio]-3-methyl--phthalide, 7-[(5-chloro-4, 6-dimethoxy-pyr imidin-2-yl)thio]-3--methyl- phthalide , 7- [ (4.6-dimethoxy-5-f luoro-pyr imid in-2-yl ) oxy ] -3 -methyl - -phthalide . 7- [ (4.6-dimethoxy-5-methyl-pyr imid in-2-yl ) oxy ] -3- -methyl-phthal ide . 7-[(5-chloro-4, 6-dimethoxy-pyr imid in-2 -yl ) oxy ] -3--methyl-pht al ide , 7- [ (4.6-dimethoxy-pyr imid in-2 -yl ) oxy] -3-methylidene--phthalide. 7- [ (4 , 6-dimethoxy-pyr imid in- 2 -yl ) oxy] -3 -propyl idene--phthalide. - 11 - 3-butylidene-7-[(4, 6-dime hoxy-pyr imid in-2-yl ) oxy ]- -phthalide , 3-ethylidene-7-[ (4, 6-dime hoxy-l.3 , 5-tr iazin-2-yl )oxy ] -phthalide, 3-methylidene-7-[(4, 6-dimethoxy-l , 3.5-triazin-2-yl)- oxy ] -phthal ide , those compounds of formula I in which W signifies a 1 2 . . . . . group c), X, Y and Y all signify oxygen, Z signifies 1 2 7 8 CH. R and R both signify methoxy, R . R and 9 14 R all signify hydrogen, R s ignif ies_Jiy_drogen and R10 signifies hydrogen, methoxy or ethoxy; 8- [ ( 4-methoxy-6-methyl-pyr imidi -2-yl)oxy]-4-methyl- -isochroman-l-one, 8- [ (4 , 6-dimethyl-pyr imidin-2-yl )thio]-3-methyl-iso- chroman-l-one , 8- [ ( 4 , 6-dimethoxy-l .3.5-triazi -2-yl) oxy ] -isochroman- -1-one , 8- [ (4 , 6-dimethoxy-l, 3,5-triazin-2-yl)oxy]-4-methyl- - isochroman-l-one , 8- [ (4.6-dimethoxy-pyr imid in-2-yl )oxy]-4-methyl-iso- chromen-l-one . 4-ethyl-8-[ (4, 6-dimethoxy-pyr imid in-2-yl ) oxy] - iso- chromen-l-one, 8- [ ( 4 , 6-dimethoxy-pyr imidin-2-yl)oxy]-3,4-dimethyl- -isochromen-l-one and 8-[ (4, 6-dime hoxy-l.3.5-triazin-2-yl)oxy]-3-methyl-iso chromen-l-one .

The process in accordance with the invention for the manufacture of the compounds of formula I comprises reacting a compound of the general formula - 12 - 1 2 14 wherein W, X, Y , Y and R have the significances given above, with a compound of the general formula wherein R . R and Z have the significances above and L signifies a leaving group.

Under the term "leaving group" (L) there is to be understood especially a halogen atom, preferably chlorine, bromine or iodine, or an in each case optionally substituted alkylthio, benzylthio, phenylthio. alkyl-sulphinyl, benzylsulphinyl , phenylsulphinyl , alkyl-sulphonyl, benzylsulphonyl, phenylsulphonyl , alkyl-sulphonyloxy , benzylsulphonyloxy , phenylsulphonyloxy or 3-alkylsulphonyl-lH-l, 2 , 4-t iazo 1- 1-y1 (e.g. 3-methyl-sulphonyl-lH-1 , 2 , 4-tr iazol-l-yl ) group. ethanesulphonyl . ethanesulphonyl and benzylsulphonyl are especially preferred among such sulphur-containing leaving groups L.

The reaction is conveniently effected in an inert diluent, in the presence of a base or a reaction--accelerating additive, and at a temperature between 0°C - 13 - and 160°C, preferably between 20°C and 100°C, or at the boiling point of the reaction mixture. As diluents there especially come into consideration organic solvents, preferably aprotic solvents such as aliphatic or cyclic ethers, e.g. dimethoxyethane and tetrahydrofuran; aliphatic ketones, e.g. acetone and 2-butanone; aliphatic nitriles, e.g. acetonitrile and propionitrile; dimethyl-formamide; dimethylacetamide ; and heteroaromatic compounds, e.g. pyridine and lutidine, and as bases there especially come into consideration alkali metal hydrides, e.g. sodium hydride and potassium hydride; alkaline earth metal hydrides, e.g. calcium hydride; alkali metal bicar bonates , e.g. sodium bicarbonate and potassium bicarbonate; alkali metal carbonates, e.g. sodium carbonate and potassium carbonate; alkaline earth metal carbonates, e.g. calcium carbonate and magnesium carbonate; aliphatic tertiary amines, e.g. triethylamine; fully-substituted amidines, e.g. diazabicycloundecene ; and basic heteroaromatics , e.g. pyridine. Especially suitable reaction-accelerating additives are crown ethers and phase transfer catalysts as well as substances which accelerate the reaction by transiently replacing the leaving group L or, where L = halogen, by activating the leaving group L. Dimethylaminopy idine is an example of the first-mentioned substances. Silver salts and copper salts such as silver nitrate and copper(I) chloride are examples of the second--named substances.

A further proceess for the manufacture of those compounds of formula I in accordance with the invention in which W signifies a group a) or b) and X and Y1 each signify oxygen comprises subjecting a compound of the general formula - 14 - and Z have the significances given above, -— to a corresponding alkylation. acylation, car bonylation, car baraoylation. halogenation. substitution. Grignard reaction or Wittig reaction analogously to the respective methods which are described hereinafter and which are used in connection with the production of the starting materials of formula II.

Further, those compounds of formula I in which X and/or Y1 signify sulphur can be manufactured by sulphurizing the corresponding compounds I in which X and/or Y1 signify oxygen.

The compounds of formula I obtained can be isolated and purified according to methods known per se.

Insofar as no planned synthesis for the isolation of pure isomers is carried out, the product can result as a mixture of two or more isomers. The isomers can be · separated according to methods known per se. If desired, pure optically active isomers can also be manufactured, for example, by synthesis from corresponding optically active starting materials. - 15 - The starting materials of formula II are partly novel, partly known. Thus, for example, 7-hydroxyphthalide and 3.7-dihydroxy-phthalide (compounds of formula II in which W signifies methylene or hydroxymethylene. X, Y1 and 2 . . 14 Y each signify oxygen and R signifies hydrogen) are known from E.L. Eliel et al., J. Org. Chem. 18., 1679 et seq. (1953). Furthermore, the production of 7-hydroxy-3- -methyl-phthalide and 3-ethyl-7-hydroxy-phthalide is described in S. Kushner et al., J.A.C.S. 75., 1097 et seq. (1953) and, respectively, J. Blair and G.T. Newbold, J. Org. Chem. 1955, 2871 et seq. A route to 3 , 7-dihydroxy-3--methyl-phthalide is also known [see Z. Horii et al..J. Pharm. Soc. Japan 74, 466 et seq. (1954)]. The novel starting materials of formula II can be produced according to methods known per se.

Those starting materials of formula II in which signifies a group a) or b) and X and Y1 both signify oxygen can be produced in a manner known per se, e.g. in accordance with Reaction Schemes 1 and 2 hereinafter: - 16 - Reaction Scheme 1 VII - 17 - Reaction Scheme 2 - 18 - In Reaction Schemes 1 and 2 above Y , R . R , R5 and R14 have the significances given above; R3 signifies optionally substituted C. ,-alkyl, C_ _- 1—0 ώ — O -alkenyl, C -alkynyl. optionally substituted phenyl or 3 II optionally substituted C. ,-alkoxy; R signifies 1— 0 optionally substituted C -alkyl. C -alkenyl, 1-6 2-3 C -alkynyl or optionally substituted phenyl; R 7 . . 14' . . . signifies C. ,-alkyl; R signifies hydrogen or 15 . . .

C. -alkyl; R signifies alkanoyl, especially . 19 .

C_ c-alkanoyl. or a group -Si(CH,)_R in which I95 16 . . .

R stands for C. ,-alkyl; R signifies hydrogen, 1— b methyl, tert. butyl or a protecting group which is usual in chemistry, such as, for example, benzyl, p-methoxybenzyl 17 . . or methoxyethoxymethyl ; R signifies hydrogen or 18 17 C. _-alkyl and R signifies C. .-alkyl or R and 18 - R together signify tetramethylene which can be substituted with a methoxy or hydroxymethyl group.

The individual reactions such as, for example, the 4 ' . ' . various Grignard reactions using R g halide, R Li, 3 ' 3 " 3 " R Mg halide, R Mg halide or R Li. the hydrolysis with concentrated sulphuric acid ("cone. H2S04"), the reduction of a ring carbonyl group (e.g. in reaction step VII→IIa) or of a hydroxy group (e.g. in reaction step IIb→IId), the oxidation using manganese dioxide ("Mn02") and the Wittig reaction will be familiar to a person skilled in the art. Thus, for example, compounds of formula VII can be produced from compounds of formula VI according to the directions of J.-A.H. Nasman, Synthesis 15 1985. 788 (in this case R signifies the 2.2-dimethyl-propanoyl group). Further, for example, compounds of formula VII can be produced from the corresponding o-nitrophthalic anhydrides according to generally known directions - see e.g. E.L. Eliel. J.A.C.S. 77., 5092 et seq. (1955). Thus, the nitro group is firstly reduced and converted into the corresponding hydroxy compound by - 19 - diazotization. Other relevant literature references relating to suitable reaction conditions for certain reaction steps are J. Blair and G.T. Newbold, J. Org.

Chem. 1955. 2871 et seq. as well as B.L. Chenard et al.t J. Org. Chem. 49.. 318 et seq. (1984).

Further, in Reaction Scheme 2 TMEDA signifies tetra-methylethylenediamine , THF signifies tetrahydrofuran, DMF signifies dimethylf ormamide and L' signifies a leaving group such as chlorine, acetyl, imidazolyl. N, O-dimethyl-hydroxylamino or dimethylamino . The preferred groups 17 18 NR R for the direct metallation in the ortho- 17 18 -position to the carboxamide function CONR R (reaction step IX→X) are diethylamino [see V. Snieckus. Heterocycles .14, 1649 et seq. (1980) J, methylamino [see S.N. Yeola and R.S. Mali, Ind. J. Chem. 25B. 804 et seq. (1986) as well as N.S. Narasimhan and R.S. Mali. Synthesis 1983 , 957 et seq.] and ter t . butylmethylamino [see D.B. Reitz and S.M. Massey. J. Org. Chem. 5J5. 1375 et seq. (1990)].

In the few cases in which the reaction conditions (RC) are not indicated in Reaction Schemes 1 and 2, namely in the case of process steps IIe→IIf and XI-XIV, the . . 3 reaction conditions depend on the nature of the group R 4 3 . . . . or R to be introduced. Where R signifies optionally substitut or option signifies g halide or convenien reagent, wh le where R s gn f es opt ona y su stituted C. ,-alkoxy, the starting material lib or lie is treated . 6 . 3 with the corresponding hydroxy compound R H, conveniently under acidic catalysis, e.g. using sulphuric acid, p-toluenesulphonic acid or trif luoroacetic acid. - 20 - Examples of the first type of reaction are described, inter alia, by J. Grandguillot and F. Roussac in Synthesis 1979 , 607 et seq., and by P. Canonne et al. in Tetrahedron Lett. 26. 4719 (1985).

With respect to reaction steps XII→IIh. XII→IIi and XIV-»IIj, it is further generally known that a phenolic methyl ether group or the corresponding thioether 16 . . . group (R signifies methyl) can be cleaved readily to 16 . . . the hydroxy or thiol group (R signifies hydrogen) with hydrogen bromide in water or glacial acetic acid, with boron tribromide or with the boron tr ibromide-dimethyl sulphide complex in methylene chloride or ethylene dichloride. Other suitable cleavage reagents are aluminium trichloride, boron trichloride, dimethylboron bromide in methylene chloride as well as alkylmercaptides , e.g. sodium ethylmercaptide in toluene or xylene. 41 Those starting materials of formula lib in which R signifies methyl or ethyl and the corresponding protected compounds can also be produced by heating a corresponding phthalic anhydride with malonic acid or methylmalonic acid in the presence of a base. e.g. t iethylamine (TEA) or pyridine (Py) , which, moreover, serves as the diluent, until the evolution of carbon dioxide has finished, namely according to the following equation: XV lib - 21 - 20 . . wherein R signifies hydrogen or methyl Further methods for the production of the starting materials of formula II are known from the specialist literature. For example, the 3-hydroxyphthalides of formula XI given in Reaction Scheme 2 can also be produced according to the teaching of B. . Trost et al., J. Org.

Chem. 45., 1835 et seq. (1980). F. Hauser & R. Lee. J. Org.

Chem. 4_5, 3061 et seq. (1980), and J.N. Freskos et al.. J. Org. Chem. 50. 805 et seq. (1985) and these can then be converted as indicated above into the corresponding starting materials of formula Ilg or I I .

In order to arrive at optically active compounds of formula Hi in the above manner, a compound of formula lib, lib1 or XIII. can be reduced in the presence of an optically active reducing agent such as, for example, the binaphthol-modif ied chiral lithium aluminium hydride reagent (R)- or (S)-BINAL-H [see R. Noyori et al., J.A.C.S. 106. 6717 et seq. (1984)] or in the presence of an optically active, chiral hydrogenation catalyst such as, for example, ruthenium [(R)- or (S)-BINAP] [see R.

Noyori et al.. J.A.C.S. 109 , 5856 et seq. (1987)].

A further variant for the production of optically active compounds of formula Hi comprises treating a chiral carbinol according to the method of Trost et al., J. Org. Chem. 45.. 1835 et seq. (1980) successively with n-butyllithium/tetramethylethylenediamine, with carbon dioxide or ethyl chlorof ormate and with hydrogen bromide in accordance with the following equation: - 22 - The starting materials of formula IX are either known or can be produced according to methods known per se.

Those starting materials of formula II in which W 3 signifies a group a) and R signifies chlorine or bromine can be produced by halogenating the corresponding 3 . . . starting materials of formula II in which R signifies hydroxy, e.g. the starting materials of formulae lib and lie given above. Especially suitable halogenating agents (chlorinating agents or brominating agents) are the corresponding thionyl halides SOHal'2. phosphorus oxyhalides POHal'^, phosphorus trihalides PHal'.. or phosphorus pentahalides PHal'^ in which Hal1 signifies chlorine or bromine. A further method for the production of such chloro-containing or bromo-containing starting materials of formula II comprises treating the 3 co responding starting materials II in which R signifies hydrogen, e.g. the starting materials of formulae Hi given above, with N-chlorosuccinimide or N-bromosuccinimide . In order to obtain the starting materials of formula II in which W signifies a group a) 3 . . . and R signifies fluorine, C. , -a Ik 1 thio , cyano or 1 — 0 rhodano. the corresponding starting materials of - 23 - formula II in which R signifies chlorine or bromine can be subjected to a halogen-exchange reaction, e.g. with an alkali metal fluoride such as sodium fluoride, with a sodium mercaptide, with sodium cyanide or with potassium rhodamide. All of these transformations can be carried out under reaction conditions which are known per se.

Those starting materials of formula II in which W . . 3 signifies a group a) and R signifies cyano can likewise be produced by treating a corresponding starting material 3 of formula II in which R signifies hydroxy, e.g. a starting material of formula lib or lie given above, with potassium cyanide or hydrocyanic acid under reaction conditions which are known per se [see, for example. J.N. Frescos et al.. J. Org. Chem. 50, 805 et seq. (1985)].

Those compounds of formula II in which W signifies a 3 . . . group a) and R signifies C2_7-car boxyalkyl (an example of "optionally substituted C -alkyl"), carboxy 1—6 or carbamoyl can be produced by the conventional 3 hydrolysis of the corresponding compounds II in which R signifies (C„ -alkoxycar bony1 ) -C. , -alkyl, C_ - Z-b 1-6 2-7 -alkoxycarbonyl or cyano.

Those compounds of formula II in which W signifies a 3 group a) and R signifies formyloxy. 5~alkanoyloxy , C -alkoxycarbonyloxy , C -alkylcar bamoyloxy or 2—5 2—3 di(C^ ^-alkyl ) carbamoyloxy can be produced by conventionally formylating, acylating, car bonylating or carbamoylating the corresponding compounds II in which R3 signifies hydroxy.

Finally, those compounds of formula II in which 3 . . . signifies a group a) and R signifies di (C1_2~alkoxy ) -phosphonyl can be produced by reacting the corresponding 3 . . . compounds II in which R signifies hydroxy with a C -alkyl phosphite. - 24 - Those starting materials of formula II in which W 1 2 . . signifies a group b), Y and Y both signify oxygen 6 . . and R signifies hydrogen can be produced, for example, in accordance with Reaction Scheme 3 hereinafter in which 5 14 16 R , R and R have the significances given above 21 22 and R and R each signify methoxy or ethoxy. - 25 - XVII XX XIX Il k - 26 - An analogous Reaction Scheme in which the individual reaction steps are illustrated is described in R.S. Mali and S.L. Patil, Synthetic Comm. .20. 167 et seq. (1990) and in E. Napolitano et al.. Syntheses 1985. 38-40.

Those starting materials of formula II in which signifies a group c) and X and Y1 signify oxygen can be produced in a manner known per se. e.g. in accordance with the methods of N.S. Narasimhan and B.H. Bhide, Tetr. 27. 6171 (1971). J. Sinha et al.. J. Ind. Chem. Soc. 6J3. 907 (1986) and H.N. Singh and R.P. Singh, J. Ind. Chem. Soc. 65 , 685 (1988) and also in accordance with Reaction Scheme 4 hereinafter: - 27 XXVII I Im ( 11 = R7 ; R12 _ D R9 ) - 28 - 2 7 8 9 10 In this Reaction Scheme Y . R , R , R , R 11 12 14 16 17 18 R . R . R . R . R , R . TMEDA. THF and L' have the significances given above and LDA signifies lithium diisopropylamide, NBS signifies N-bromosuccinimide and L" signifies a leaving group such as halogen, especially chlorine, or 2-imidazolyl .

The individual reactions which are involved in this Reaction Scheme are also known per se.

Those starting materials of formula II in which W signifies a group d) and X and Y1 signify oxygen can also be produced in accordance with the methods of N.L. Lewis et al.. Synthesis 1986. 944 and F.M. Hauser et al.. J. Org. Chem. 53.. 4676 (1988).

In general, those starting materials of formula II in which X and/or Y1 signify oxygen can be converted into the corresponding starting materials of formula II in which X and/or Y1 signify sulphur by sulphu ization methods which are known per se [see e.g. N. Lozach, Sulfur Reports 9_. 153 et seq. (1980)]. For the sulphur ization there is coveniently used phosphorus pentasulphide . optionally in the presence of pyridine, e.g. as the phosphorus pentasulphide-pyr idine (1:2) complex, the Lawesson reagent 2.4-bis- ( 4-methoxyphenyl ) -1 , 2-dithioxo--1.3.2 , 4-dithiaphosphetane [see e.g. S.-O. Lawesson et al.. Bull. Soc. Chim. Belg. 87., 229-238 (1978)] or the Davy reagent 2 , 4-bis- (methylthio ) -1.3.2.4-dithiadi-phosphetane (see e.g. Sulfur Lett. 1983, 1. 167). whereby this is preferably used in a stoichiometric amount or in slight excess (e.g. up to 20%). This reaction is conveniently carried out in an inert organic diluent such as an optionally halogenated aromatic, e.g. toluene or dichlorobenzene . or an aliphatic or cyclic ether, e.g. dimethoxyethane , and at elevated temperature, especially - 29 - at temperatures between 80°C and the reflux temperature of the reaction mixture. Moreover, a catalytic amount, i.e. about 0.1 to 10 weight percent based on the amount of the compound II, of hexamethylphosphor ic acid triaraide is advantageously added. This procedure is especially suitable for the production of those compounds of formula II in which X signifies oxygen and Y1 signifies sulphu .

Those starting materials of formula II in which X signifies sulphur and Y1 signifies oxygen can also be produced, for example, by converting a hydroxy compound of formula XII (see Reaction Scheme 2) or XXV (see Reaction Scheme 4) or a compound of formula XXII (see Reaction Scheme 4) in accordance with transformation reactions, such as halogenation and sulphur ization, which are known to a person skilled in the art into the corresponding thiol compound and subsequently lactonizing to the compound of formula II: - 30 - Reaction Schemp ς I In - 31 - 4 In this Reaction Scheme R and R in the 3 " 4 7 8 compound XXVIII signify R and R or R and R depending on whether the compound is prepared from a compound of formula XII or from a compound of formula XXII. 2 Those starting materials of formula II in which Y signifies sulphur can be produced - unless already obtainable in accordance with the methods described previously (see, for example. Reaction Schemes 2, 4 and 5) - in a manner known per se, e.g. in accordance with Reaction Scheme 6 hereinafter in which W, X, Y1 and 14 . . .

R have the significances given above: - 32 - Reaction Scheme 6 25 30 - 33 - In the above Reaction Schemes 1-6 and equations (XV→IIb); XVI→IIi') the products of formulae Ila-IIq are sub-groups of starting materials of formula II. The starting materials of formulae IV, V, IX, XV. XVI and XVII are either known or can be produced according to methods known per se.

The starting materials of formula III are for the most part known and the novel starting materials III can be produced analogously to the known starting materials III.

The compounds of formula I (referred to hereinafter as compounds in accordance with the invention or active ingredients) have herbicidal properties and are suitable for the control of weeds, including weed grasses, inter alia Agropyron repens, Alopecurus myosuroides, Avena fatua, Bromus inermis, Echinochloa crus-galli, Poa annua. Sorghum halepense. Abutilon theophrasti, Amaranthus retroflexus. Cassia obtusifolia, Chenopodium album, Galium aparine, Matricaria chamomilla, Sinapsis arvensis and Stellaria media, in diverse crops, inter alia rice (especially aquatic rice), wheat, soya, rape, corn and cotton crops. Moreover, the compounds are not only pre-emergence . but also post-emergence herbicides. A good selectivity, e.g. in the control of weeds, especially weed grasses, in soya and cotton crops, has been shown in the case of certain representatives of the compounds I.

Furthermore, the compounds in accordance with the invention have plant growth regulating properties and are suitable as active substances for positively influencing the growth of crops. This effect can not only bring about a desired inhibition of growth in crops, but can also sufficiently inhibit weeds after their germination in order to eliminate them as competitors of the crops. This is of advantage and accordingly extremely desirable having - 34 - regard to the ecological relationship. In particular, there can be mentioned here the protection of the soil surface from drying-out and/or erosion as well as the prevention of a stock of weed seeds in the soil (with simultaneous prevention of the flowering and the renewed self-seeding) . Therefore, under certain circumstances this activity provides the advantage of the prevention of weed germination which is complete, but possibly limited in time .

In practice, a concentration of 1 g to 3 kg of compound in accordance with the invention/ha, preferably 10 g to 1 kg of compound in accordance with the invention/ha, is usually sufficient to achieve the desired herbicidal effect. In order to achieve the desired herbicidal effect with optimal crop tolerance, the range of 10 to 100 g/ha is especially favourable in the pre-emergence treatment and the range of 100 to 1000 g/ha is especially favourable in the post-emergence treatment.

The weed control composition in accordance with the invention contains an effective amount of at least one compound of formula I, as defined above, as well as formulation adjuvants. The composition conveniently contains at least one of the following formulation adjuvants: solid carrier substances; solvents or dispersion media; tensides (wetting and emulsifying agents); dispersing agents (without tenside action); and stabilizers. With the use of these and other adjuvants these compounds, namely the herbicidally active substances, can be converted into the usual formulations such as dusts, powders, granulates, solutions, emulsions, suspensions, emulsifiable concentrates, pastes and the like. - 35 - The compounds of formula I are generally insoluble in water and can be formulated according to methods which are usual for water-insoluble compounds using the respective formulation adjuvants. The manufacture of the compositions can be carried out in a manner known per se, e.g. by mixing the respective active ingredient with solid carrier substances, by dissolution or suspension in suitable solvents or dispersion media, if necessary using tensides as wetting or emulsifying agents and/or dispersing agents, by diluting pre-prepared emulsifiable concentrates with solvents or dispersion media etc.

As solid carrier substances there essentially come into consideration: natural mineral substances such as chalk, dolomite, limestone, aluminas and silicic acid and salts thereof (for example siliceous earth, kaolin, bentonite, talc, attapulgite and montmorillonite) ; synthetic mineral substances such as highly dispersible silicic acid, aluminium oxide and silicates; organic substances such as cellulose, starch, urea and synthetic resins; and fertilizers such as phosphates and nitrates, whereby such carrier substances can be present e.g. as powders or as granulates.

As solvents or dispersion media there essentially come into consideration; aromatics such as benzene, toluene, xylenes and alkylnaphthalenes ; chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes , chloroethylenes and methylene chloride; aliphatic hydro-carbons such as cyclohexane and paraffins, e.g. petroleum fractions; alcohols such as butanol and glycol, as well as their ethers and esters; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone ; and strongly polar solvents or dispersion media such as dimethylformamide , N-methylpyrrolidone and dimethyl sulphoxide. such solvents preferably having flash points - 36 - of at least 30°C and boiling points of at least 50°C. and water. Among the solvents or dispersion media there also come into consideration so-called liquified gaseous extenders or carrier substances, which are those products which are gaseous at room temperature and under normal pressure. Examples of such products are especially aerosol propellants such as halogenated hydrocarbons, e.g. dichlorodif luoromethane . If the weed control composition in accordance with the invention is present in the form of a pressurized pack, then a solvent is conveniently used in addition to the propellant.

The tensides (wetting and emulsifying agents) can be non-ionic compounds such as condensation products of fatty acids, fatty alcohols or fatty-substituted phenols with ethylene oxide; fatty acid esters and ethers of sugars or polyvalent alcohols; the products which are obtained from sugars or polyvalent alcohols by condensation with ethylene oxide; block polymers of ethylene oxide and propylene oxide; or alkyldimethylamine oxides.

The tensides can also be anionic compounds such as soaps; fatty sulphate esters, e.g. dodecyl sodium sulphate, octadecyl sodium sulphate and cetyl sodium sulphate; alkyl sulphonates, aryl sulphonates and fatty--aromatic sulphonates such as alkylbenzenesulphonates , e.g. calcium dodecylbenzenesulphonate , and butyl naphthalenesulphonates ; and more complex fatty sulphonates, e.g. the amide condensation products of oleic acid and N-methyltaur ine and the sodium sulphonate of dioctyl succinate.

Finally, the tensides can be cationic compounds such as alkyldimethylbenzylammonium chlorides, dialkyldimethyl-ammonium chlorides, alkyltr imethylammonium chlorides and ethoxylated quaternary ammonium chlorides. - 37 - As dispersing agents (without tenside action) there essentially come into consideration; lignin, sodium and ammonium salts of lignin sulphonic acids, sodium salts of maleic anhydride-diisobutylene copolymers, sodium and ammonium salts of sulphonated polycondensation products of naphthalene and formaldehyde, and sulphite lyes.

As dispersing agents, which are especially suitable as thickening or anti-settling agents, there can be used e.g. methylcellulose , carboxymethylcellulose. hydroxyethyl-cellulose, polyvinyl alcohol, alginates, caseinates and blood albumin.

Examples of suitable stabilizers are acid-binding agents, e.g. epichlorohydr in, phenyl glycidyl ether and soya epoxides; antioxidants, e.g. gallic acid esters and butylhydroxytoluene ; UV-absor bers , e.g. substituted benzo-phenones, diphenylacrylonitr ile acid esters and cinnamic acid esters; and deactivators, e.g. salts of ethylene-diaminotetraacetic acid and polyglycols.

The weed control compositions in accordance with the invention can contain, in addition to the active ingredient in accordance with the invention, synergists and other active ingredients, e.g. insecticides, acaricides, fungicides, plant growth regulators and fertilizers. Such combination compositions are suitable for intensifying the activity or for broadening the spectrum of activity.

The weed control compositions in accordance with the invention generally contain between 0.001 and 95 weight percent, preferably between 0.5 and 75 weight percent, of one or more compounds in accordance with the invention as the active ingredient ( s ) . They can be present e.g. in a form which is suitable for storage and transport. In such - 38 - formulations, e.g. emulsifiable concentrates, the active ingredient concentration is normally in the higher range, preferably between 1 and 50 weight percent, especially between 5 and 30 weight percent. These formulations can then be diluted, e.g. with the same or different inert substances, to give active ingredient concentrations which are suitable for practical use, i.e. preferably about 0.001 to 10 weight percent, especially about 0.005 to 5 weight percent. The active ingredient concentrations can, however, also be smaller or greater.

As mentioned above, the manufacture of the weed control compositions in accordance with the invention can be carried out in a manner known per se.

For the manufacture of pulverous preparations the active ingredient, i.e. at least one compound in accordance with the invention, can be mixed with a solid carrier substance, e.g. by grinding together; or the solid carrier substance can be impregnated with a solution or suspension of the active ingredient and then the solvent or dispersion medium can be removed by evaporation, heating or sucking-off under reduced pressure. By adding tensides or dispersing agents such pulverous preparations can be made readily wettable with water, so that they can be converted into aqueous suspensions which are suitable e.g. as spray compositions.

The active ingredient can also be mixed with a tenside and a solid carrier substance to form a wettable powder which is dispersible in water, or it can be mixed with a solid pre-granulated carrier substance to form a product in the form of a granulate.

When desired, the active ingredient can be dissolved in a water- immiscible solvent such as. for example, a - 39 - high-boiling hydrocarbon, which conveniently contains dissolved emulsifying agent, so that the solution becomes self-emulsif ing upon addition to water. Alternatively, the active ingredient can be mixed with an emulsifying agent and the mixture can then be diluted with water to the desired concentration. Moreover, the active ingredient can be dissolved in a solvent and thereafter the solution can be mixed with an emulsifying agent. Such a mixture can likewise be diluted with water to the desired concentration. In this manner there are obtained emulsifiable concentrates or ready-f or-use emulsions.

The use of the weed control compositions in accordance with the invention, which forms a further object of the present invention, can be carried out according to usual application methods such as sprinkling, spraying, dusting, watering or scattering. The method in accordance with the invention for the control of weeds comprises treating the locus to be protected against weeds and/or the weeds with a compound in accordance with the invention or with a weed control composition in accordance with the invention.

The following Examples serve to illustrate the invention in more detail.

I . Manufacture of the compounds of formula I: Example 1 7- Γ ( , 6-Dimethoxy-py imidin-2-yl )oxyl-3-methyl-phthalide A mixture of 0.4 g of 7-hydroxy-3-methyl-phthalide, 0.52 g of 4 , 6-dimethoxy-pyr imid ine-2-methyl sulphone and 1.05 g of potassium carbonate in 5 ml of dimethylf ormamide is heated at reflux temperature for 2 hours. Subsequently, the mixture is diluted with ethyl acetate and washed once - 40 - with water and once with sodium chloride solution. The crude product remaining after evaporation of the solvent is purified by chromatography on silica gel with ethyl acetate/n-hexane (1:2). In this manner there is obtained 7-[ (4.6-dimethoxy-pyr imidin-2-yl ) oxy] -3-methyl-phthalide , m.p. 190-191°C; IR spectrum (CHC13): C=0 1765 cm"1; ■"■H-NMR (CDC13. 200 MHz): 7.84 ppm (double-d, J1=J2=8Hz .1H) . 7.57 ppm (d, J=8Hz.1H) . 7.37 ppm (d, J=8Hz.1H) , 6.01 ppm (S.IH). 5.72 ppm (q . J=7Hz .1H) . 3.73 ppm (s,6H of the two OCH3), 1.56 ppm (d , J=7Hz , 3H) .

Examples 2-81 The corresponding compounds of formulae II and III are reacted with each other analogously to the procedure described in Example 1 (in some cases using acetonitrile or tetrahydrofuran as the solvent and sodium hydride as the base) in order to manufacture the compounds of formula I listed in Tables 1-5 hereinafter: - 41 - Table 1 - 42 - 2-Methoxy-ethoxy H 0 H M.p. 95-96°C Methyl H 0 4-Chloro M.p. 145-148°C Methyl H 0 4-Bromo M.p. 147-149°C n-Propyl H 0 H M.p. 94-95°C n-Butyl H 0 H M.p. 94-95°C Ethynyl H 0 H Nitromethyl H 0 H M.p. 150-152°C Methoxy-carbonyl H 0 H Fluoro H 0 H 2-Dimethyl-araino-ethoxy H 0 H 2-Methylthio-ethoxy H 0 H n-Butoxy H 0 H (N-Methylcar-bamoyDraethoxy H 0 H Acetyloxy H 0 H Ethoxycar-bonyloxy H 0 H Hydroxy Trifluoro - methyl 0 H M.p. 234-235°C - 43 - Table 2 1 2 3 Example Z R R R Physical data 38 CH Methyl Methyl Methyl M.p. 163-164°C; IR(CHC13): C=0 1770 cm"1 39 CH Ethoxy Ethoxy Methyl M.p. 99-100°C; IR(CHC1 ): -1 C=0 1765 cm 40 CH Me hoxy Methyl Methyl M.p. 148-149°C; IR(CHCl3): C=0 1765 cm 1 41 c-ci Methoxy Me hoxy Methyl M.p. 195-196°C 42 CH Trifluoro- methyl Methoxy Methyl M.p. 114-117°C 43 CH Chloro Me hoxy Methyl M.p. 149-150°C 44 CH Isopro- poxy Me hoxy Methyl M.p. 79-82°C 45 CH Methoxy Methyl Methoxy M.p. 107°C 46 CH n-Pro- poxy Me hoxy Methyl M.p. 108-109°C 47 CH Chloro Difluoro- methoxy Methyl M.p. 114-117°C 46 CH Chloro Dimethyl- amino Methyl M.p. 180-183°C 49 CH Methyl 2,2,2- Trifluoro- ethoxy j Methyl M.p. 79-81°C - 44 - CH Chloro Methyl- amino Methyl M. p. 185 -188 °C CH H Methoxy Methyl M. p. 110 -112 °C CH Methoxy Ethoxy Methyl M. p. 113 -116 °C CH Chloro Methoxy Methoxy M. p. 114 -115 °C CH Methoxy- methyl Methoxy Methyl M. p. 76-78°C CH Dif luoro - methoxy Methoxy Methyl M. p. 108 -109 °C CH Methoxy N-Methoxy — methyl- aitiino Methyl M. p. 106 -108 °C CH Methoxy Ethyl- amino Methyl M. p. 143 -146 °C 45 - Table 3 2 1 2 3 Example Y R R R Physical data 58 0 Methoxy Methoxy Methyl M. p. 133 -134°C 59 0 Methoxy Methoxy Methoxy M. p. 88- 90°C 60 S Methoxy Methoxy Methyl M. p. 150 -151°C 61 0 Chloro Methyl Methyl M. p. 144 -147°C 62 0 Methoxy Dimethyl- amino Methyl M.p. 148 -151°C 63 0 Methyl Methoxy Methyl M. p. 148 -151°C 64 0 Methoxy Methyl- amino Methyl M.p. 179 -182°C 65 0 Chloro Methyl- amino Methyl M. p. 181 -183°C 66 0 Methoxy Methoxy Ethyl M.p. 137 -140°C 67 0 Chloro Methoxy Methyl M.p. 139 -142°C - 46 - Table 4 5 6 Example R R Physical data 68 Methyl H ( Z-isome ) M.p. 165-167°C; IR (CHC1 ) : C=0 1765 1H-NMR (CDC13): 5.69 ppm (q. J=7Hz, CH= ) 69 Methyl Methyl ( Z-isomer ) M.p. 193-196°C; IR (CHC1 ): C=0 1768 cm 70 4-Methoxy- (E-isomer ) M.p. 231-233°C; phenyl H 1H-NMR (CDC13): 6.99 ppm (s, CH=) 71 Phenyl H (Z-isomer) M.p. 191-192°C; 1H-NMR (CDC13): 6.46 ppm (s, CH=) 72 3-Methox} ( Z-isome ) M.p. 144-147°C; phenyl H 1H- MR (CDC13): 6.43 ppm (S. CH=) 73 Ethyl H (Z-isomer ) M.p. 122-125°C; ■""H- R (CDC13): 5.64 ppm (t, J=7Hz, CH= ) 74 n-Propyl H ( Z-isomer ) M.p. 115-11B°C; 1H-NMR (CDC13): 5.66 ppm (t, J=8Hz, CH= ) 75 H H - 47 - Table 5 7 8 9 10 Example Z -CR R -CR R - Physical data 76 CH -CH2CH(CH3)- M.p. 180-182°C; IR(CHC1 ) : C=0 1728 -1 cm 77 N -CH2CH(CH3)- M.p. 140-143°C 78 CH -CH2CH(C2H5)- M.p. 78-80°C 79 CH -CH(CH3)CH(CH3)- (trans form) 1H-NMR (CDC13): 4.38 ppm (m, IH) 80 CH CH(CH )CH(CH )- (cis form) LH-NMR (CDC13): 4.68 ppm (ra. IH) 81 CH CH(CH3)CH2- M.p. 116-119°C - 48 - Example 82 8- Γ ( .6-Dimethoxy-pyr imidin-2-yl ) oxy 1 -3-methyl-isochromen--1-one 8-Hydroxy-3-methyl-isochromen-l-one is reacted with 4 , 6-dimethoxy-pyr imidine-2-methyl sulphone analogously to the procedure described in Example 1 in order to manufacture 8-[ (4, 6-dimethoxy-pyr imidin-2-yl ) oxy ] -3--methyl-isochromen-l-one , m.p. 188-190°C.

Example 83 3-r(Z)-Ethylidenel-7-C(4.6-dimethoxy-py imidin-2 -yl ) oxy 1 --phthalide 350 mg (2 mmol) of 7-hydroxy-3-vinyl-phthalide. 460 mg (2.2 mmol) of 4 , 6-dimethoxy-2-methylsulphonyl--pyrimidine and 414 mg (3 mmol) of potassium carbonate are heated at 100°C in 10 ml of dimethylformamide for one hour. Then, the reaction mixture is poured into 100 ml of semi-concentrated sodium chloride solution and the aqueous mixture is extracted twice with 50 ml of ethyl acetate. The organic phase is dried over anhydrous magnesium sulphate, concentrated under reduced pressure and the crude product is subjected to a chromatographic purification on silica gel with ethyl acetate/n-hexane (2:3).

In this manner there are obtained 250 mg of 3-[(Z)--ethyl idene ) -7- [ (4, 6-dimethoxy-pyrimidin-2-yl)oxy]--p thalide in the form of colourless crystals, m.p. 163-165°C; IR spectrum (CHC13): C=0 1765 cm-1. This product is identical with the compound of Example 68. - 49 - Example 84 7- Γ (4.6-Dimethoxy-py imidin-2-yl ) oxy 1-3-hydroxy-phthalide a) 15.2 g of 7-[ (4, 6-dimethoxy-pyr imidin-2-yl ) oxy ] -3--methoxyphthalide (see Example 8) is heated at reflux temperature for 3 hours in a 1:1 mixture of tetrahydro-furan and hydrochloric acid. The mixture is then concentrated under reduced pressure and the separated crystals are filtered off and washed with water. There is obtained pure 7-[ (4, 6-dimethoxy-pyrimidin-2-yl)oxy]-3--hydroxy-phthalide. m.p. 143-145°C; IR (KBr): 1770 cm-1; i-NMR (CDC13): 6.60 ppm (s. 1H) . b) The above product can also be manufactured by dissolving 6 g of 3.7-dihydroxy-phthalide in a methanolic solution of 2.6 g of potassium hydroxide and evaporating the resulting solution to dryness azeotropically with toluene. The monopotass ium salt is then taken up in 100 ml of dry dimethyl sulphoxide and treated portionwise with 1.9 g of sodium hydride. The mixture is stirred at 40°C for a further 10 minutes, then treated at room temperature with 9.9 g of 4 , 6-diraethoxy-pyr imidinyl-2-methyl sulphone and held at 30-35°C for a further 1 hour. The mixture is treated with water and extracted with ethyl acetate in order to remove impurities. The aqueous phase is acidified with hydrochloric acid and then extracted with fresh ethyl acetate. After treatment with active charcoal and/or filtration on silica gel there is thus obtained the 7-[ (4, 6-dimethoxy-pyrimidin-2-yl)oxy]-3-hydroxy-phthalide, m.p. 144-146°C. as light yellowish crystals. - 50 - Example 85 3 -Chioro-7- Γ ( .6-dimethoxy-pyr imidin-2-yl ) oxy 1 -phthalide 2.3 g of 7- [ (.4 , 6-dimethoxy-pyr imidin-2-yl ) oxy ] -3- -hydroxy-phthalide (see Example 84) are suspended in about 40 ml of phosphorus oxychloride and the suspension is heated at 90°C for 2 hours. The reaction mixture is then introduced into 250 ml of water at 35-45°C. The mixture is then diluted with a further 500 ml of water and the separated crystals are filtered off and washed neutral with water. Pure 3-chloro-7- [ (4 , 6-dimethoxy-pyr imidin-2--yl ) ox ] -phthalide , m.p. 143-144°C, is obtained as light yellowish crystals.

Example 86 7-Γ (4.6-Dimethoxy-pyr imidin-2-yl )ox ]-3-f luor o-phtha 1 ide A mixture of 1.0 g of 3-chlor o-7- [ ( 4 , 6-d imethoxy- -pyrimidin-2-yl)oxy]-phthalide (see Example 85) and 0.19 g of spray-dried potassium fluoride as well as a spatula tip of 18-crown-6 is heated at reflux temperature for 100 minutes. The mixture is then filtered over Celite®, the filtrate is evaporated and the crude product is recrystallized from ethyl acetate/n-hexane. There is thus obtained 7-[ (4, 6-dimethoxy-pyr imid in- 2-yl ) oxy] -3 -f luoro--phthalide, m.p. 172-174°C.

Example 87 7- Γ (4 , 6-Dimethoxy-pyr imid in-2-yl )oxy]-3-meth lthio- -phthalide 1.0 g of 3-chloro-7-[ (4, 6-dimethoxy-pyr imid in-2-yl ) -oxy ] -phthal ide (see Example 85) and 0.24 g of sodium - 51 - methylmercaptide are stirred in 20 ml of tetra ydrofuran for about 16 hours. Subsequently, the mixture is filtered through Celite® and the filtrate is evaporated under reduced pressure. By recrystallization from diethyl ether/n-hexane there is obtained 7- [ ( 4 , 6-dimethoxy--py imidin-2-yl )oxy]-3-methylthio-pht alide, m.p. 138-140°C.

Example 88 3-Ethylthio-7-r(4, 6-dimethoxy-pyr imidin-2-yl ) oxyl -phthalide Analogously to the method described above (Example 87), from 3-chloro-7- [ (4 , 6-dimethoxy-pyr imidin-2--yl ) oxyj -phthalide (see Example 85) and sodium ethyl-mercaptide there is obtained 3-ethylthio-7- [ ( 4 , 6--dimethoxy-pyrimidin-2-yl)oxy]-phthalide, m.p. 103-106°C.

Example 89 7- Γ ( 4.6-Dimethoxy-pyr imidin-2-yl ) oxyl -3- hoda o-phthalide A mixture of 1.4 g of 3-chloro-7-[ (4.6-dimethoxy--pyrimidin-2-yl)oxy]-phthalide (see Example 85) and 0.46 g of potassium rhodanide is heated in 15 ml of acetonitrile for 4 hours in the presence of a spatula tip of 18-crown-6. The mixture is filtered through Celite®, the filtrate is evaporated and the residue is chromatographed using 30% ethyl acetate/n-hexane. 7- [ (4 , 6-Dimethoxy--pyrimidin-2-yl)oxy]-3-rhodano-phthalide, m.p. 161-163°C, is obtained as pale yellow crystals. - 52 - Example 90 7- Γ ( , 6-Dimethoxy-pyr imidin-2-yl ) oxy 1 -3-phenoxy-pht alide A mixture of 1.4 g of 3-chloro-7- [ (4 , 6-dimethoxy- -pyrimidin-2-yl)oxy]-phthalide (see Example 85) and 0.63 g of potassium phenolate is heated at reflux temperature in 15 ml of acetonitrile in the presence of a spatula tip of 18-crown-6. After 19 hours the mixture is filtered through Celite®, the filtrate is evaporated and the crude product is purified by column chromatography (eluent 25% ethyl acetate/n-hexane ) . 7- [( 4 , 6-Dimethoxy-py imidin-2--yl)oxy]-3-phenoxy-phthalide, m.p. 155-157°C, is obtained as white crystals.

Example 91 7- Γ ( 4 , 6-Dimethoxy-py imid in-2-yl ) oxy 1 -3-vinyl-phthal ide 3.6 g of 7-[ (4.6-dimethoxy-pyr imidin-2-yl ) oxy] -3- -hydroxy-phthal ide (see Example 84) are placed in 60 ml of absolute tetrahydrofuran at -45°C and the solution is treated within 10 minutes with 18 ml of a 2M solution of vinylmagnes ium chloride in tetrahydrofuran . The mixture is stirred at room temperature for about 16 hours, a further 6 ml of vinylmagnes ium chloride solution are added thereto and the mixture is heated at reflux temperature for a further one hour. Then, the cooled reaction solution is acidified with IN hydrochloric acid and freed from tetra-hydrofuran on a rotary evaporator. The aqueous phase is then extracted with tert. butyl methyl ether and the organic phase is washed and evaporated under reduced pressure. After chromatography on silica gel with ethyl acetate/n-hexane (2:3) as the eluent there is obtained pure 7- [ ( 4 , 6-d ime thoxy-pyr imidin-2-yl ) ox ] -3-vinyl--phthalide, m.p. 94-97°C. - 53 - Example 92 3-Cyano-7- Γ ( .6-dimethoxy-pyr imidin-2-yl ) oxy 1 -phthalide 1.0 g of 7-[ (4.6-dimethoxy-pyr imidin-2-yl ) oxy] -3- -hydroxy-phthal ide (see Example 84) is introduced into a solution of 2.1 g of potassium cyanide in 15 ml of water and the mixture is treated dropwise with 10 ml of concentrated hydrochloric acid over 10 minutes at -7 to -3°C. The mixture is stirred at room temperature for about 16 hours and the separated crystals are then filtered off. They are rinsed with water and recrystallized from acetone/n-hexane . There is obtained 0.2 g of 3-carbamoyl--7-[ (4, 6-dimethoxy-pyrimidin-2-yl)oxy]-phthalide (see also Example 17 ) .

The mother liguor is chromatographed using ethyl acetate/n-hexane (1:1) as the eluent. Pure 3-cyano-7--[ (4, 6-d imethoxy-pyr imid in-2-yl) oxy] -phthalide, m.p. 157-159°C. is obtained.

Example 93 3-Cyanomethoxy-7- [ (4.6-dimethoxy-py imid in-2-yl ) oxy 1 --phthalide A mixture of 1.5 g of 7- [( 4 , 6-dimethoxy-py imidin-2--yl)oxy]-3-hydroxy-phthalide (see Example 84) and 0.8 ml of chloroacetonitr ile in ethyl methyl ketone is held at 60°C for 1 hour in the presence of 2.1 g of dry potassium carbonate and a spatula tip each of sodium iodide and 18-crown-6. The cooled reaction mixture is taken up in tert. butyl methyl ether and the solution is washed with dilute hydrochloric acid and water, evaporated and purified by chromatography on silica gel (eluent: ethyl acetate/n-hexane 1:1). There is thus obtained 3-cyano- - 54 - methoxy-7- [ ( 4 , 6-dimethoxy-pyr imi din- 2 -yl ) oxy ] -phthal ide , m.p. 99-102°C.

Example 94 7- Γ (4 , 6-Dimethoxy-pyr imidin-2-yl ) oxy ] -3- (methox car bonyl-methoxy) -pht al ide Analogously to the method described above (Example 93), from 7- [( 4 , 6-dimethoxy-pyr imidin-2-yl ) oxy ] --3-hydroxy-phthalide (see Example 84) and methyl chloro-acetate there is obtained 7-[ (4, 6-dimethoxy-pyr imidin-2--yl ) oxy ] -3- (methoxycar bonylmethox ) -phthal ide , m.p. 102-104°C.

Example 95 3 -Ac etoxy- 7- [ (4 , 6-dimethoxy-pyr imid in- 2-yl )ox 1-phthalide 1-3 g of 7- [( 4 , 6-dimethoxy-pyr imidin-2-yl ) ox ] -3- -hydroxy-phthalide (see Example 84) are dissolved in 30 ml of tetrahydrofuran and the solution is treated with 0.6 ml of t iethylamine and then dropwise at 25°C (internal temperature) with 0.5 ml of acetyl chloride. After stirring at room temperature for 2 hours the mixture is extracted with ethyl acetate against ice-water and dilute hydrochloric acid, the organic phase is washed with sodium chloride solution, dried over anhydrous magnesium sulphate and evaporated under reduced pressure. By column chromato-graphy on silica gel [eluent: ethyl acetate/n-hexane (2:3)] there is obtained 3-acetoxy-7- [ ( 4 , 6-d imethoxy--pyrimidin-2-yl)oxy]-phthalide. m.p. 119-120°C, as a white crystals . - 55 - Example 96 3- (Et oxycar bonylmethyl ) -7- f ( 4.6-dimethoxy-pyr imid in-2--yl )oxy ]-phthalide A mixture of 1.5 g of 7- [ ( 4.6-dimethoxy-py imidin-2--yl ) ox ] -3-hydroxy-phthal ide (see Example 84) and 2.5 g of (ethoxycarbonylmethylene)-triphenyl-phosphorane in about 40 ml of tetrahydrofuran is held at reflux temperature for 10 hours. The solvent is then evaporated and the reaction product remaining behind is purified on a silica gel column (eluent: ethyl acetate/n-hexane 1:1). There is thus obtained 3- (ethoxycar bonylmethyl ) -7- [ (4 , 6-dimethoxy--pyrimidin-2-yl)oxy]-phthalide, m.p. 150-152°C.

Example 97 3- (Dime thoxyphos phony1 ) -7- f ( , 6-dimethoxy-pyr imid in-2--yl )oxyl-phthalide 1.0 g of 7-[ (4.6-dimethoxy-pyrimidin-2-yl)oxy]-3--hydroxy-phthalide (see Example 84) is dissolved in 30 ml of methanol, 0.88 ml of 5. M sodium methylate solution is added and then the mixture is treated dropwise with 0.43 ml of dimethyl phosphite. The mixture is left at room temperature for one hour and then 0.33 ml of methane-sulphonic acid is added thereto and the reaction mixture is evaporated under reduced pressure. The residue is taken up in ethyl acetate and the solution is washed once with 2N hydrochloric acid and once with sodium chloride solution. The organic solution is treated with active charcoal and the product is recrystallized from ethyl acetate/n-hexane. There is obtained 3- (dimethoxy-phosphonyl ) -7- [ ( .6-dimethoxy-pyr imid in- 2 -y 1 ) oxy ] --phthalide. 1H- MR (CDC13): 5.70 ppm (d. llHz, 1H) . 3.93 and 3.64 ppm (2d. 11Hz. P(O) (OCH ) ) ; m.p. 135-137°C. - 56 - Example 98 7- Γ ( 4 , 6-Dimethoxy-pyr imidin-2-yl ) oxy 1 -3-methyl-2-benzo-thiophen- K 3H) -one 1.21 g of 7-hydroxy-3-methyl-isobenzofuran-l(3H)--thione in 10 ml of acetonitrile are heated at reflux temperature for 2 hours together with 0.83 g of 4 , 6-dimethoxy-py imidinyl-2-methyl sulphone and 1.05 g of potassium carbonate in the presence of a spatula tip of 18-crown-6. The reaction mixture is taken up in ethyl acetate and the organic solution is washed with water and sodium chloride solution, evaporated under reduced pressure and then purified by chromatography (eluent: 30% diethyl ether in n-hexane) . There is obtained as yellowish crystals 7-[ (4.6-dimethoxy-pyr imidin-2-yl ) oxy] -3-methyl-2--benzothiophen-l(3H)-one, m.p. 157-159°C; IR spectrum (CHC13): 1682. 1600. 1555. 1356. 1240. 1190 cm"1; ■""H-N R (CDC1 ): 4.86 ppm (q. 1H) . 1.78 ppm (d. 3H) .

Example 99 7- Γ (4.6-Dimethoxy-pyr imid in- 2 -yl )oxy]-3-methyl-isobenzo-furan-l(3H)-thione A mixture of 6.35 g of 7- [( 4 , 6-dimethoxy-py imid in- -2-yl)oxy]-3-methyl-phthalide (see Example 1) and 8.92 g of 2 , 4- bis- ( 4-me hoxyphenyl )-2,4-dithioxo-l,3,2,4- -dithiadiphosphetane (Lawesson reagent) in 40 ml of xylene is held at reflux temperature for about 16 hours. The reaction mixture is then filtered over silica gel (eluent: 30% diethyl ether /n-hexane ) and recrystallized from ethyl acetate/n-hexane . There is thus obtained as yellow crystals 7-[(4.6-dimethoxy-pyr imidi -2-yl)oxy]-3--methyl-isobenzofuran-l(3H)-thione. m.p. 163-164°C; IR -1 spectrum (CHC13): 1602. 1570. 1358. 1304. 1195 cm ; 1H- MR (CDC1 ): 5.80 ppm (q. 1H) . 1.71 ppm (d. 3H) . - 57 - Example 100 7-Γ (4, 6-Dimethoxy-l , 3.5- tr iaz in-2-y1) oxy 1 -3 -methyl- sobenzo-furan-l(3H)-thione 1.0 g of 7-hydroxy-3-methyl-isobenzofuran-1 ( 3H) --thione is introduced into a suspension of 0.15 g of sodium hydride in absolute dimethylformamide and, after the evolution of hydrogen has finished, treated with 1.0 g of 2-chloro- , 6-dimethoxy-l , 3 , 5- tr iazine . The mixture is stirred at room temperature for 5 hours, ice-water is then added thereto, the mixture is extracted with ethyl acetate and washed with sodium chloride solution. The evaporated crude product is purified by chromatography (eluent: 45% ethyl acetate in n-hexane) and recrystallized from acetone/n-hexane . There is thus obtained as yellow crystals 7-[ (4, 6-dimethoxy-l, 3 , 5-t iazin-2-yl)oxy]-3- -methyl-isobenzofuran-l(3H)-thione. m.p. 177-178°C; IR -1 spectrum (CHC1 ): 1590. 1560, 1366, 1304, 1140 cm ; 1H-NMR (CDC13): 5.81 ppm (q. IH) , 1.73 ppm (d, 3H) . 11. Production of the starting materials of formula II Example 101 7-Hydroxy-3-methyl-phthalide (i) 12.5 ml of methyllithium ( 1.6M in diethyl ether) are added dropwise within 30 minutes under argon at -78°C to a solution of 5.32 g of 1- (2.2-dimethylpropanoyloxy) -3.5- -dioxo-exo-10-oxatr icyclo [5.2.1.0(2,6)]dec-8-ene (compound 141 . . . 15 of formula VI in which R signifies hydrogen and R signifies 2 , 2-dimethylpropanoylox ) in 50 ml of absolute tetrahydrofuran. After completion of the addition the mixture is left to come to room temperature and is then poured into 100 ml of ice-cold saturated monopotassium - 58 - phosphate solution. The aqueous solution is extracted three times with diethyl ether and the combined organic phases are washed with monopotassium phosphate solution, dried over anhydrous magnesium sulphate and, after decolo ization with active charcoal, filtered and concentrated. The yellow coloured crude product is recrystallized from diethyl ether /n-hexane . In this manner there are obtained 1.8 g (32% of the theoretical yield) of ( 3aa, 4β , 7β , 7aa) -hexahydro-l-hydr oxy-l-methyl-3-oxo--4 , 7-epoxyisobenzofuran-4-yl pivalate as yellowish crystals, m.p. 153-154°C (= compound of formula VIII in 41 . . . 14 ' which R signifies methyl, R signifies hydrogen 15 . . . and R signifies 2.2-dimethylpropanoyloxy ) . (ii) 1.7 g of the product of the previous reaction step are added at 2-4°C under argon to a suspension of 0.31 g of sodium borohydride in 40 ml of absolute ethanol. After the addition has been effected the mixture is left to come to room temperature and poured into 60 ml of IN hydro-chloric acid. The ethanol is evaporated off under reduced pressure, the resulting white crystals are filtered off and rinsed with water and dried. In this manner there is obtained 0.87 g (86% of the theoretical yield) of ( 3 act, 4J3.7 Si.7aa) - hexahydro-l-me thy1-3-0X0-4 , 7-epoxy-isobenzofuran-4-yl pivalate as colourless crystals, m.p. 114-115°C. (iii) 11.4 g of the product of the previous reaction step are added portionwise to 30 ml of concentrated sulphuric acid cooled with ethanol/ice. After the addition has been effected the mixture is poured onto ice and the separated crystals are then filtered off and rinsed with water until neutral. In this manner there are obtained 6.4 g (91% of the theoretical yield) of 7-hydroxy-3-methyl-phthalide as beige crystals, m.p. 107-108°C. - 59 - Example 102 3 , 3-Dimethyl-7-hydroxy-phthalide (i) A Grignard solution prepared from 1.43 g of magnesium and 8.37 g of methyl iodide in 65 ml of diethyl ether is added dropwise to a solution of 7.85 g of 1- (2.2-dimethyl-propanoyloxy)-3 , 5-dioxo-exo-10-oxatr icyclo[ 5.2.1.0(2,6)-dec-8-ene in 35 ml of tetrahyd ofuran in such a manner that the temperature does not exceed -25°C. After completion of the addition the reaction mixture is stirred at room temperature for several hours, then acidified to pH 2 with 2N hydrochloric acid and extracted with diethyl ether. After drying the ether solution and evaporating the solvent there remain 7.5 g of crude product which is subsequently purified by chromatography on silica gel with diethyl ether/n-hexane (3:1). In this manner there is obtained (3aa, 4β,7β.7aa) -hexahydro-1 , 1-dimethy1-3 -oxo-- , 7-epoxyisobenzofuran-4-yl pivalate as an oil. (ii) The oily product of the previous reaction step is taken up in 2.8 ml of concentrated sulphuric acid and the solution is stirred at 5°C for 20 minutes. The solution is then poured on to ice and extracted with diethyl ether. The organic phase is washed with water, dried over anhydrous magnesium sulphate and evaporated. In this manner there is obtained 3 , 3-dimethyl-7-hydroxy-phthalide as colourless crystals, m.p. 128-134°C.

Example 103 3-Ethyl-7-hyd oxy-pht alide (i) 13.7 ml of sec . butyl 1 i thium ( 1.4M in cyclohexane/ isopentane) are added dropwise to a solution of 5.2 g of 2-methoxy-N,N-diethyl-benzamide and 2.91 g of tetra- - 60 - methylethylenediamine in 50 ml of absolute tetrahydrofuran in such a manner that the temperature does not exceed -68°C. After the addition has been effected the reaction mixture is stirred at -78°C for a further hour and 2.5 ml of propionaldehyde are subsequently added thereto. The reaction mixture is left to come to room temperature slowly, stirred for one hour and diluted with 300 ml of diethyl ether. The organic phase is washed with 2N hydrochloric acid and thereafter with saturated sodium chloride solution, dried over anhydrous magnesium sulphate and evaporated. In this manner there is obtained 6-(l--hydroxyethyl ) -2-methoxy-N, N-diethyl-benzamide as a crude product . (ii) The crude product of the previous reaction step is taken up in 48% aqueous hydrogen bromide and the solution is heated at reflux temperature for about 16 hours. The mixture is then cooled to room temperature and extracted twice with diethyl ether. After drying over anhydrous magnesium sulphate and evaporation there remains a crude product which is subsequently purified by chromatography on silica gel with diethyl ethe /n-hexane (1:4). In this manner there is obtained 3-ethyl-7-hydroxy-phthalide , IR spectrum (CHC13): C=0 1738 cm-1.

Example 104 7-Hydroxy-3-isopropyl-phthalide (i) A solution of 8.0 g of 1- (2 , 2-dimethylpropanoyloxy) --3 , 5-dioxo-exo-10-oxatr icyclo [5.2.1.0(2.6)]dec-8-ene in 25 ml of tetrahydrofuran is added dropwise to a Grignard solution of 6.8 g of isopropylmagnesium chloride in 33 ml of tetrahyd ofuran in such a manner that the temperature does not exceed -20°C. After the addition has been effected the reaction mixture is left to come to room - 61 - temperature and stirred for about 16 hours. The pH value of the mixture is brought to 2 with 45 ml of 2N hydrochloric acid while cooling with ice and the mixture is extracted twice with 300 ml of diethyl ether. The organic phase is dried over anhydrous magnesium sulphate, evaporated under reduced pressure and the resulting crude product is purified by chromatography on silica gel with diethyl ether /n-hexane (3:7). In this manner there is obtained ( 3aa.4B .7β .7aa) -hexahydro-l-isopropyl-3-oxo--4 , 7-epoxyisobenzofuran-4-yl pivalate. (ii) The product of the previous reaction step is introduced into concentrated sulphuric acid and the solution is stirred at 5°C for 20 minutes. The mixture is then poured on to ice and extracted with diethyl ether. After drying and evaporation of the ether solution there is obtained 7-hydroxy-3-isopropyl-phthalide as colourless crystals .

Example 105 3.7-Dihydroxyphthalide 4.4 g of 3-hydroxy-7-methoxy-phthalide [see B.L. Chenard et al.. J. Org. Chem. 49. 318 (1984) for its preparation] are heated to reflux temperature for 75 minutes in 100 ml of 48% hydrobromic acid.

Subsequently, the mixture is poured on to ice-water and the aqueous mixture is extracted four times with ethyl acetate. The combined organic phases are washed with sodium chloride solution, dried over anhydrous magnesium sulphate and concentrated under reduced pressure. The crude product is filtered through a short silica gel column with ethyl acetate as the eluent and the thus--obtained brown oil is decolorized by heating in the presence of active charcoal. In this manner there are - 62 - obtained 2.5 g of a yellowish, amorphous solid, i.e. the crude 3.7-dihydroxyphthalide , which, if necessary, can be used without purification for the production of a further starting material of formula II, e.g. 7-hydroxy-3-methoxy--phthalide (see Example 118).

Example 106 3.7-Pihydroxyphthalide The title compound can also be produced as follows 3.0 g of 3-hydroxy-7-methoxy-phtha 1 ide [see B.L.

Chenard et al.. J. Org. Chem. 9. 318 (1984)] are introduced portionwise into a suspension of 8.2 g of aluminium trichloride in 50 ml of methylene chloride while holding the internal temperature at 27°C. The mixture is stirred at room temperature for a further 5 hours, then poured into 200 ml of ice-cold IN hydrochloric acid and extracted three times with 200 ml of ethyl acetate each time. The organic solution is washed with sodium chloride solution and dried over anhydrous magnesium sulphate.

After evaporation of the solvent and recrystallization from ethyl acetate and n-hexane there is obtained pure 3 , 7-dihydroxyphthalide . m.p. 124-126°C.

Example 107 3.3-Piisopropyl-7-hydroxy-phthalide Analogously to the procedure described in Example 102, starting from 1- ( 2 , 2-dimethylpropanoyloxy) -3 , 5-dioxo-exo--10-oxatr icyclo [ 5.2.1.0( 2 , 6 ) ] dec-8-ene and isopropyl-magnesium iodide via ( 3aa, β , 7β .7aa) -hexahydro-1 , 1--di isopropyl-3-oxo-4 , 7-epoxyisobenzofuran-4-yl pivalate there is obtained 3.3-diisopropyl-7-hydroxy-phthalide . - 63 - Examples 108-117 The starting materials of formula Ilh' or Hi" given in Table 6 hereinafter are obtained analogously to the procedure described in Example 103 starting from 2-methoxy-N.N-diethyl-benzamide, butyllithium and the 3 " 4 respective aldehyde or ketone R R CO (see Reaction Scheme 2 ) : Hi" - 64 - Table 6 Example 118 7-Hydroxy- 3 -methoxy-phthal ide A solution of 2.5 g of 3 , 7-dihydroxyphthalide (as a crude product - see Examples 105 and 106) in 70 ml of methanol is treated with 4 drops of concentrated sulphuric acid and, after the subsequent addition of 3A molecular sieve, left to stand for about 16 hours. The mixture is then filtered and the filtrate is evaporated. The crude product. 3 g of yellow oil, is purified by chromatography - 65 - (flash chromatography) on silica gel using ethyl acetate/ n-hexane (3:7). In this manner there are obtained 1.9 g (70% of the theoretical yield) of 7-hydroxy-3-methoxy--phthalide as reddish crystals, m.p. 77-79°C (after crystallization from diethyl ether/n-hexane ) ; IR spectrum (CHC13) : C=0 1745 cm"1.

Examples 119-129 The starting materials of formula lie1 or Ilf1 listed in Table 7 hereinafter are obtained analogously to the procedure described in Example 118 from 3 , 7-d ihydroxy-phthalide or 3.7-dihydroxy-3-methyl-phthalide and the respective hydroxy compound in the presence of a catalytic amount of sulphuric acid: Ilf - 66 - Table 7 Example 130 7-Hydroxy- 3 -me hoxy- 3 -me hy 1-phthalide The title compound (also see Example 123) can also be produced as follows: 1.5 g of 3-hydroxy-7-methoxy-3-methyl-phthalide (see Example 131 hereinafter) in 50 ml of methanol saturated - 67 - with hydrogen chloride are left to stand at room temperature for one hour and the mixture is thereafter taken up in ethyl acetate and washed with ice-cold sodium chloride solution. After removal of the solvent there is obtained 3 , 7-dimethoxy-3-methyl-phthalide , m.p. 101-104°C. 1.45 g of the above product in 20 ml of methylene chloride are stirred for 45 minutes with 3.4 g of aluminium trichloride and the mixture is then treated with ice-water and extracted twice with methylene chloride. The organic phase is dried over anhydrous magnesium sulphate and concentrated under reduced pressure. There is thus obtained 7-hydroxy-3-methoxy-3-methyl-phthalide . m.p. 106-109°C; IR spectrum (CHC13). C=0 1740 cm"1.

Example 131 3.7-Dihydroxy-3-methyl-phtha 1 ide 5.4 g of 3-methoxy-phthalic anhydride [see A.V.R. Rao et al., Indian J. Chem. 20B, 248 et seq. (1981)], 4.7 g of malonic acid and 9 ml of tr iethylamine are heated slowly. The suspension is stirrable at 55°C and a moderately strong evolution of CO^ takes place from 68°C. The internal temperature is held at 73°C until the evolution of gas has finished (about 1 hour) and the mixture is then heated at reflux temperature (internal temperature 85°C) for a further 4 hours. The cooled reaction mixture is extracted with ethyl acetate against water. The aqueous phase is then adjusted to pH 1.7 and extracted three times with fresh ethyl acetate, dried over anhydrous sodium sulphate and evaporated under reduced pressure. By fractional crystallization (ethyl acetate/n-hexane) there is obtained 3-hydroxy-7-methoxy-3-methyl-phthalide, m.p. 156-158°C; IR spectrum (CHC1 ) : C=0 1772 cm"1. 1.9 g of the above product are dissolved in 20 ml of methylene chloride and the solution is treated at -70°C - 68 - with 3.5 g of boron tribromide. The mixture is then taken up in ice-cold dilute hydrochloric acid and the organic phase is extracted with ethyl acetate, dried over anhydrous sodium sulphate and evaporated under reduced pressure. In this manner there is obtained as an amorphous solid crude 3 , 7-dihydroxy-3-methyl-phthalide which, if necessary, can be used in impure form for the production of a further starting material of formula II (e.g. 7-hydroxy-3-methoxy-3-methyl-phthalide) .

Example 132 4-Hydroxy-l , 3-dihydro-3-oxo-l- isobenzofurancar boxamide 2.8 g of 3.7-dihydroxy-phtha 1 ide (see Examples 105 and 106) are introduced into a solution of 7.5 g of potassium cyanide in 35 ml of water and the mixture is treated slowly with 25 ml of concentrated hydrochloric acid while cooling with ice so that the internal temperature does not rise above 10°C. The reaction mixture is held at room temperature for a further 5 hours and the crystals are then filtered off. The product (m.p. 213-215°C), which is washed with water and dried well, is pure 4-hydroxy-l , 3--dihydro- 3 -oxo-1- isobenzofurancar boxamide .

Example 133 7-Hydroxy- 3- tr if luoromethyl-phtha 1 ide A mixture of 26.4 g of N,N-dimethyl-2-methoxy- -benzamide and 19 ml of tetramethylethylenediamine in 120 ml of absolute tetrahydrofuran is treated at -70°C with 100 ml of a 1.4 molar solution of sec . butyl 1 ithium in cyclohexane/isooctane and. after 45 minutes, treated dropwise within 20 minutes with 27.3 ml of ethyl trif luoroacetoacetate . The mixture is left to come to room - 69 - temperature for about 16 hours, treated with 200 ml of water and acidified to pH 2 with hydrochloric acid. The mixture is extracted with a total of 600 ml of diethyl ether and the organic phase is dried over anhydrous magnesium sulphate and evaporated under reduced pressure. The residue is chromatographed on silica gel (eluent: ethyl acetate/ n-hexane 1:1). In this manner there is obtained 3-hydroxy- -7-methoxy-3- t if luoromethyl-phthal ide . I - spectrum (CHC13): C=0 1785 cm"1. 11.1 g of the above product in 140 ml of ethanol are treated portionwise at room temperature with 1.5 g of sodium borohydride. The mixture is taken up in ice-water containing hydrochloric acid and extracted with fresh diethyl ether. After removal of the solvent and subsequent chromatography there is obtained pure 7-methoxy-3--trif luoromethyl-phthalide, IR spectrum (CHC1 ) : C=0 1785 cm-1. 4.6 g of the above product in 30 ml of tetrahydrofuran are treated dropwise at -70°C with 7.0 g of boron tribromide. The mixture is left to come to room temperature slowly and is then extracted with ethyl acetate against ice-water. The solvents are removed and the crude product is filtered over silica gel (eluent: ethyl acetate/n-hexane 1:1). There is obtained crystalline 7-hydroxy-3- tr if luoromethyl-phthalide, IR spectrum (CHC13): C=0 1766 cm"1; """H- MR (CDC1..): 5.68 ppm (q. 6 Hz. 1H) .

Example 134 3 , 7-Pihydroxy-3-tr if luoromethyl-phthalide The title compound can be produced analogously to the above Example (133) from 3-hydroxy-7-methoxy-3-tr if luoro- - 70 - methyl-phthalide (see Example 133) and boron tribromide; m.p. 128-129°C.

Example 135 7-Merea to- 3-methyl-ph halide 24 g of 7-hydroxy-3-methylphthalide are introduced into an aqueous solution of 8.2 g of potassium hydroxide in 130 ml of water and the mixture is then treated dropwise with 23.5 g of dimethylcarbamoyl chloride while stirring well and cooling. After 90 minutes the mixture is adjusted to pH 11 with sodium hydroxide solution, added to ice and extracted twice with ethyl acetate. After drying and evaporating off the solvent as well as recrystallization from ethyl acetate and n-hexane there is obtained O- ( 1.3 -dihydro- 3 -methy1-1-oxo-7-isobenzofuranyl ) -dimethylthiocarbamate. m.p. 163-164°C. 26 g of the above product are taken up in 180 ml of resorcinol dimethyl ether and the mixture is heated at 212°C for 24 hours. The cooled reaction mixture is filtered through silica gel with ethyl acetate/n-hexane (2:1) as the eluent and, after removal of the solvent, recrystallized . There is obtained S- ( 1 , 3-dihydro-3-methyl--l-oxo-7-isobenzofuranyl ) -dimethylthiocarbamate. m.p. 144-145°C. 18.4 g of the above product in a mixture of 120 ml of methanol and 60 ml of chloroform are treated with a solution of 4.2 g of sodium in 180 ml of methanol. The mixture is stirred at room temperature for about 3 hours and then 390 ml of ethyl acetate are added thereto. Most of the solvents is now removed under reduced pressure and the residue is extracted with ethyl acetate against saturated sodium chloride solution. By filtration - 71 - over silica gel (eluent: ethyl acetate/n-hexane 1:2) there is obtained pure 7-mercapto-3-methyl-phthalide. m.p. 40°C.

Example 136 7-Hydroxy-3-methyl-isobenzofu an-1 ( 3H)-thione 3.9 g of 7-hydroxy-3-methyl-phthalide (see Examples 101 and 111) and 5.1 g of Lawesson reagent in 20 ml of xylene are heated at 140°C for 4 hours. By chromato-graphical filtration of the mixture through silica gel [eluent: ethyl acetate/n-hexane (1:9)] there is obtained 7-hydroxy-3-methyl-isobenzofuran-1 (3H)-thione, m.p. 39-41°C; IR spectrum (CHC1 ) : C=0 1624, 1604. 1368. 1330. 1304. 1165 cm" ; mass spectrum: 180 (M+=100) , 165(58). 137(24).

Example 137 7-Hydroxy-3-vi yl-phthal ide 600 mg of 3.7-dihydroxy-phthalide (see Examples 105 and 106) are stirred at -78°C in 20 ml of absolute tetrahydrofuran . 6 ml of a 2 vinylmagnes ium chloride solution in tetrahydrofuran are then added under an argon atmosphere using a syringe. The reaction mixture is left to come to room temperature and poured into 100 ml of IN hydrochloric acid. The mixture is subseguently extracted twice with 75 ml of ethyl acetate each time and the combined organic phases are washed with sodium chloride solution, dried with anhydrous magnesium sulphate and the organic solution is concentrated under reduced pressure. There remain 600 mg of crude product which is subjected to flash chromatog aphy on silica gel with ethyl acetate/ n-hexane (1:1). - 72 - In this manner there are obtained 380 mg (60% of the theoretical yield) of 7-hydroxy-3-vinyl-phthal ide .

Example 138 7-Hydroxy-3-isopropylidene-phthal ide (i) Analogously to the procedure described in Example 104, 10 g of 1- ( 2 , 2-dimethylpropanoylox ) -3 , 5-dioxo-exo-10--oxatr icyclo [ 5.2.1.0(2 , 6 ) ] dec-8-ene are placed in 25 ml of tetrahydrofuran at -35°C and the solution is then treated with 3.9 g of isopropylmagnes ium chloride in 30 ml of tetrahydrofuran. The mixture is left to come to room temperature. 27 ml of 2N hydrochloric acid are then added thereto, the mixture is extracted twice with diethyl ether, the organic phase is dried over anhydrous magnesium sulphate and evaporated. In this manner there is obtained (3aa, 4β.7β, 7aa) -hexahydro-l-hydroxy-l-isopropyl-3--oxo- , 7-epoxyisobenzofuran-4-y1 pivalate as a crude product. (ii) The thus-obtained crude product is taken up in concentrated sulphuric acid at 0°C and the solution is stirred for 20 minutes. The solution is subseguently poured on to ice, the agueous mixture is extracted with diethyl ether and the organic phase is dried over anhydrous magnesium sulphate. The oily crude product is subseguently separated by chromatography using a 20% solution of diethyl ether in n-hexane. In this manner there is obtained 7-hydroxy-3-isopropylidene-phthalide as a solid which is not characterized further. - 73 - Example 139 ( Z ) -3-Ethylidene-7-hydroxy-phthalide To a solution of 3.6 g of sodium in 130 ml of methanol are added drop ise under nitrogen at 0-10°C 14.5 ml of dimethylphosphite and 20 g of 3-hydroxy-7-methoxy--phthalide (see Example 118) are simultaneously introduced portion ise. The mixture is then stirred at room temperature for 30 minutes and 11.3 ml of methanesulphonic acid are then added thereto within 10 minutes. After a further hour most of the methanol is distilled off under reduced pressure, the residue is poured onto 400 ml of dilute hydrochloric acid and ice and the aqueous mixture is extracted three times with 900 ml of ethyl acetate. The organic phase is washed with sodium chloride solution, dried over anhydrous magnesium sulphate, evaporated under reduced pressure and the residue is recrystallized from ethyl acetate/n-hexane . In this manner there is obtained pure 3-dimethoxyphosphonyl-7-raethoxy- -phthalide, m.p. 129-131°C. 12.3 g of the above product are dissolved in 750 ml of dry tetrahydrofuran and the solution is treated at 3°C with 5.2 g of potassium te t . butylate . After stirring for one hour at this temperature 2.8 ml of acetaldehyde are added dropwise and the reaction mixture is stirred at 12°C for a further hour. The mixture is, as above, poured onto dilute hydrochloric acid and ice and extracted with ethyl acetate, and the organic phase is washed with water and with sodium chloride solution, dried over anhydrous magnesium sulphate and evaporated under reduced pressure. By filtration through silica gel [eluent: ethyl acetate/ n-hexane 7:3)] there is obtained as an (E/Z) mixture crude 7-methoxy-3-ethylidene-phthalide, 1H-NMR (CDC13): 5.88 ppm and 5.64 ppm (2q, J=7,5 Hz, (E) and (Z) CH=). An - 74 - initial fraction contains pure (Z)-7-methoxy-3-ethylidene--phthalide, m.p. 106-109°C. 1.1 g of the above product together with 2.8 g of aluminium trichloride in 50 ml of methylene chloride are stirred at room temperature for 2 hours and the mixture is then poured into ice-cold, dilute hydrochloric acid and extracted with methylene chloride. The organic phase is washed with semi-saturated sodium chloride solution, dried over anhydrous magnesium sulphate and concentrated under reduced pressure. In this manner there is obtained pure (Z)-3-ethylidene-7-hydroxy-phthalide. 1H-NMR (CDC1 ): 5.70 ppm (q, J =7. 5Hz. CH= ) .

Examples 140-144 The starting materials of formula Ilk' given in Table 8 hereinafter are obtained analogously to the procedure described in Example 139 from 3-hydroxy-7--methoxy-phthalide via 3-dimethoxyphosphonyl-7-methoxy--phthalide, which is reacted with the respective aldehyde to give the corresponding compound XIX which, in turn, is treated with aluminium trichloride (see Reaction Scheme 3: XVII→XVIII→XIX→IIk) .

HCR5 Ilk - 75 - Table 8 5 Example R Physical data 140 Ethyl ■""H-NMR (CDC13): 5.89 and 5.66 ppm [2q. J =8Hz. (E) and (z; CH=] 141 4-Methoxy- 1H-NMR (CDC13): 6.40 ppm phenyl (s. CH=) 142 Phenyl """H-NMR (CDC13): 6.45 ppm (s, CH=) 143 3-Methoxy- """H-NMR (CDC13): 6.43 ppm phenyl (s. CH=) 144 n-Propyl """H-NMR (CDC13): 5.90 and 5.67 ppm [2q, J =8Hz , (E) and (Z) CH=] Example 145 3.4-Dihydro-8-hydroxy-4-methyl-lH-2-benzopyran-l-one 39.5 g of N,N-dimethyl-2-methoxy-benzamide and 28.5 ml of tetramethylethylenediamine are placed in 190 ml of absolute tetrahyd ofuran and the mixture is lithiated at -70°C with 150 ml of a 1.4 molar sec . -butyllithium solution in cyclohexane/ isopentane . After stirring at -70°C for 45 minutes 25.6 ml of ethyl bromide are added dropwise within 25 minutes and the reaction mixture is then left to come to room temperature slowly. The mixture is then treated with water, adjusted to pH 2 with hydrochloric acid and extracted twice with diethyl ether. The residue is purified on silica gel with ethyl acetate/ n-hexane (4:6). There is obtained as a colourless oil - 76 - 6-ethyl-N. N-d imethy1-2-me hoxy-benzamide , H-NMR (CDC13): 3.82 ppm (m) , 3.40 ppm (m) and 3.12 ppm (2q.

N(CH CH ) ), 2.56 ppm (m. CH CH ). 2 3 2 2 3 5.8 g of the above product and 3.5 g of tetramethyl-ethylenediamine in 150 ml of absolute tetrahydrofuran are lithiated at -70°C with 24.8 ml of 1.4 molar sec. -butyl-lithium solution in cyclohexane/isooctane and, after 1 hour, treated with 3 g of freshly sublimed formaldehyde. The mixture is left to come to room temperature slowly, 30 ml of concentrated hydrochloric acid are added thereto (pH 1.5) and the mixture is extracted twice with ethyl acetate. The solvents are then removed under reduced pressure. The residual oily product is taken up in 150 ml of 48% hydrobromic acid and the mixture is heated at reflux temperature for 6 hours. The mixture is extracted with fresh ethyl acetate, washed with dilute sodium bicarbonate solution, dried over anhydrous magnesium sulphate and evaporated under reduced pressure. The residual product is chromatographed (eluent: ethyl acetate/n-hexane 1:3). There is obtained as a yellow oil 3 , -dihyd o-8-hydroxy-4-methyl-lH-2-benzopyran-l-one . 1H- R (CDC13): 4.56 and 4.27 ppm (2q, 7x11 Hz, 2H) , 3.14 ppm (m. 1H) , 1.36 ppm (d. 7 Hz, CH3 ) .

Example 146 . cis- and trans-3 , 4-Dihydro-8-hydroxy-3 , 4-dimethyl-lH-2--benzopyran-l-one The 3,4-trans- and cis-3.4-dihydro-8-hydroxy-3 , 4- -dimethyl-lH-2-benzopyran-l-ones , IR spectrum (CHC1 ) : -1 1675 cm , used for the manufacture of the compounds of Examples 79 and 80 can be produced from 6-ethyl-N, N--dimethyl-2-methoxy-benzamide and acetaldehyde analogously to the procedure described in Example 143. - 77 - Example 147 7-Hydroxy-3 -methyl- isobenzofuran-1 ( 3H)-thione 1.67 g of 7-hydroxy-3-methyl-phthalide (see Example 101) and 2.17 g of 2 , -bis- ( 4-methoxyphenyl ) -2.4--dithioxo-1.3 , 2.4-dithiadiphosphetane (La esson reagent) in 8 ml of xylene are heated at 138°C for 3 hours. The cooled reaction mixture is filtered directly over a silica gel column [eluent: ethyl acetate/n-hexane (1:4)] in order to isolate the 7-hydroxy-3-methyl- isobenzofuran-1 ( 3H) - -thione; m.p. 38-40°C; IR spectrum: 1624, 1604, 1368, -1 + 1330. 1304, 1165 cm ; mass spectrum: 180 (M =100). 165 (58). 137 (24).

III. Formulation Examples Example 148 The components listed hereinafter are mixed with one another for the manufacture of a 25% spray powder: Weight percent Compound in accordance with the invention (active ingredient) 25 Silicic acid, hydrated (carrier material, milling aid) 20 Sodium lauryl sulphate (wetting agent) 2 Sodium lignosulphonate (dispersing agent) 4 Kaolin (carrier material) 49 100 Firstly, the liquid or molten active ingredient is added to the silicic acid placed in a milling aggregate. - 78 - Subsequently, the further components are admixed and the mixture is finely milled using a pinned disk mill or comparable milling aggregate.

Upon stirring in water the resulting spray powder gives a fine suspension which is suitable as a ready-for--use spray liquor.

Compounds in accordance with the invention which are liquid or which have a low melting point, i.e. up to about 100°C, are especially suitable as the active ingredient in this formulation.

Example 149 Compounds in accordance with the invention having high melting points, i.e. from about 100°C. can preferably be used as active ingredients in concentrated spray powders, e.g. as follows: Weight percent Compound in accordance with the invention (active ingredient) 75 Silicic acid, hydrated (carrier material, milling aid) 1 Alkylnaphthalenesulphonate and alkylca boxylate sulphate as the sodium salts, e.g. Morwett® EFW (De Soto) [wetting agent] 2 Sulphonated naphtha lene-forma Idehyde condensate as the sodium salt, e.g.

Morwett® D-425 (De Soto) [dispersing agent ] 10 Polyvinylpyrrolidone, e.g. PVP (GAF Corp.) [binding agent] 1 Kaolin (carrier material) 11 - 79 - The components are mixed with one another and finely-milled using a pinned disk mill or comparable milling aggregate. Upon stirring in water the resulting spray powder gives a fine suspension of any desired concentration, which is suitable as a ready-for-use spray liquor .

Example 150 A spray powder, which is based on the above Formulation Example (149), can also be converted into a dispersible granulate. For this purpose, the milled powder is sprayed in a suitable granulating apparatus (e.g. plate granulator. mixing drum, intensive mixer or fluidized bed granulator) with an aqueous solution of the binding agent until an agglomerates have formed. Thereafter, the water which has been added is removed in a drying process and the granulates are sieved to the desired size. Compared with the spray powder, the resulting granulate has various advantages (no dust formation upon application, easier dosability thanks to improved flow properties). The application is effected after stirring the preparation in water and. after complete disintegration of the granulate into the primary particles, is exactly the same as in the case of the spray powder.

Example 151 The compounds in accordance with the invention have limited solubility in conventional organic solvents.

Accordingly, only emulsifiable concentrates of relatively low concentration are possible; for example: Compound in accordance with the invention (active ingredient) 125 g/1 Soprophor®BSU (emulsifier. - 80 - Rhone-Poulenc ) 300 g/1 N-Methyl-2-pyrrolidone (solvent) 1000 ml The active ingredient and the emulsifier are introduced into the solvent while stirring and the mixture is stirred until a homogeneous solution results.

The resulting emulsifiable concentrate can be emulsified in water and then gives a ready-for-use spray liquor having the desired concentration.

Example 152 Compounds in accordance with the invention having melting point from about 60°C can also be formulated so-called suspension concentrates ( "f lowables " ) , for example : Compound in accordance with the invention (active ingredient) Ethylene glycol (frost protectant) Silicic acid (anti-settling agent) Xanthan gum. e.g. Kelzan® (Kelco) [thickening agent] Silicon anti-foam agent e.g.

Rhodorsil® 426 (Rhone-Poulenc) Nony1 henol-po lyethoxylate (wetting agent ) Sulphonated naphthalene- formaldehyde condensate as the sodium salt, e.g.

Morwett® D-425 (De Soto) (dispersing agent ) Water ad The formulation adjuvants are dissolved in water. The pre-milled active ingredient is dispersed in the solution - 81 - while stirring. The resulting coarse suspension is now subjected to a wet milling (e.g. in a colloid mill, stirring ball mill). If desired, further additives such as anti-foam agents, anti-settling agents and biocides can now be added in small amounts.

For use, the resulting "flowable" can, if desired, be diluted with water and then gives a ready-for-use spray liquor of the desired concentration.

Claims (22)

- 82 - Claims

1. Compounds of the general formula whe ein W signifies one of the divalent groups a)-d) .11 .12 R' d) - C = C - 1 2 X. Y and Y each signify oxygen or sulphur. . . . 13 Z signifies CR or nitrogen, R1 signifies hydrogen, fluorine, chlorine. C ^ _ ^ - -alkyl, halomethyl, methoxymethy1. C 3-alkoxy, dif luoromethoxy or methylthio. 2 . . . R signifies methyl, C1_2-alkoxy, C1_2-fluoro- alkoxy, C^ 2-alkylamino , di(C^ 2~alkyl ) amino or N-methoxymethylamino , - 83 - signifies hydrogen, fluorine, chlorine, bromine, optionally substituted C. -alkyl, C_ -alkenyl, 1—6 2—3 ?2 3-alkynyl, optionally substituted phenyl, hydroxy, optionally substituted C -alkoxy, 1—6 C -alkylthio, phenoxy, phenylthio, cyano, 1—6 rhodano, formyl, carboxy, C -alkoxycar bonyl , 2—5 carbamoyl, formyloxy. C -alkanoyloxy , C - 2—5 2—5 -alkoxycarbonyloxy , 3-alkylcarbamoyloxy , di(C1 2~alkyl ) car bamoyloxy or di(C1 2~alkoxy)- phosphonyl , signifies hydrogen. C. ,-alkyl or tr if luoromethyl , 1—0 signifies hydrogen, C, ,-alkyl or optionally JL— 6 substituted phenyl, signifies hydrogen or methyl, 8 9 . . and R each independently signify hydrogen or C1_3-al"kyl. signifies hydrogen or C -alkoxy. 12 . . and R each independently signify hydrogen or C1_3-alkyl. signifies hydrogen, fluorine, chlorine or methyl signifies hydrogen, halogen, C -alkyl or C -alkoxy.

2. Compounds according to claim 1, wherein 3 . . . signifies a group a) and R signifies hydrogen, fluorine, chlorine, bromine, optionally substituted C. ,-alkyl. C_ .-alkenyl. C_ -alkynyl. optionally 1 — 6 £. — o Δ — i substituted phenyl, hydroxy. C -alkoxy. C -alkyl- 1—6 1- 6 thio. phenoxy. phenylthio. cyano or C -alkoxycarbony1 2 3 and R signifies hydrogen or C. ,-alkyl or R 1—6 signifies hydrogen, fluorine, chlorine, bromine, C - 1-6 -alkyl, hydroxy, C -alkoxy, C -alkylthio, phenoxy, 1-6 1-6 phenylthio or cyano and R signifies trif luoromethyl ; or 5 6 w signifies a group b), c) or d) in which R , R , 7 8 9 10 11 12 R , R , R . R , R and R have the - 84 - significances given in claim 1; and X signifies oxygen, 1 2 . . . Y , Y and Z have the significances given in claim 1 and R1 signifies fluorine, chlorine, ^ -alkyl. f luoromethyl , methoxymethyl , C -alkoxy, difluoro- 2 methoxy or methylthio. R signifies methyl, C- - 14 -alkoxy or C1_2-f luoroalkoxy and R signifies hydrogen. 3. Compounds according to claim l. wherein W

3. . . 3 . . . signifies a group a) in which R signifies hydrogen, vinyl, ethynyl, hydroxy. 4-alkoxy, C ■ 2~alkoxy substituted with halogen, vinyl, ethynyl, c 2~alkoxy, cyano. carboxy or C2 3-alkoxycar bonyl , C -alkylthio. cyano, car boxymethyl . C -alkoxycarbonyl-methyl or 4 carbamoyl and R signifies hydrogen or C-^-alkyl.

4. Compounds according to claim 1, wherein W . . . . 5 . . . signifies a group b) in which R signifies hydrogen or 6 . . . C1_3-alkyl and R signifies hydrogen.

5. Compounds according to claim 1, wherein W . . 7 8 9 signifies a group c) in which R , R and R each signify hydrogen or methyl.

6. Compounds according to claim 1, wherein W 11 12 signifies a group d) in which R and R each signify hydrogen or methyl.

7. Compounds according to any one of claims wherein X and Y each signify oxygen.

8. Compounds according to any one of claims 2 . . . wherein Y signifies oxygen.

9. Compounds according to any one of claims wherein Z signifies CH or nitrogen. - 85 -

10. Compounds according to any one of claims l to 9» wherein R signifies hydrogen, chlorine, methyl, methoxy 2 . . . or dif luoromethoxy and R signifies methoxy. ethoxy, methylamino, dimethylamino or N-methoxymethylamino .

11. Compounds according to any one of claims l to 10, 1 2 . . . wherein at least one of R and R signifies methoxy.

12. Compounds according to any one of claims 1 to 11, 14 wherein R signifies hydrogen.

13. A compound according to claim 1, selected from the group 7- [ ( , 6-dimethoxy-pyr imidin-2-yl ) oxy ] - 3 -me thy1- -phthalide, 7- [ (4 , 6-dimethoxy-pyr imidin-2-yl ) oxy] -phthai ide, 3-ethyl-7-[ (4, 6-dimethoxy-pyrimidin-2-yl)oxy]--phthalide, 7-[ (4, 6-dimethoxy-pyrimidin-2-yl)oxy]-3-isopropyl- -phthalide, 7- [ ( , 6-dimethoxy-pyr imid in-2-yl ) oxyJ - 3 -met oxy--phthalide , 7- [ ( 4-methoxy-6-methyl-pyr imid in-2-yl ) oxy] - 3 -meth 1--phthalide, -phthalide, 3-e hoxy-7- [ ( , 6-dimethoxy-pyr imidin-2-yl)oxy]--phthalide. 7- [ (4 , 6-dimethoxy-pyr imid in-2-yl ) oxy] - 3 -methoxy-3 --methyl-phthal ide , - 86 - 7- [ ( 4 -chlo o- 6 -methoxy-pyr imidin-2-yl ) oxy ] -3 -me thy1--phthalide , 7- [ (4-ethoxy-6-methoxy-pyr imidin-2-yl ) oxy J -3 -me thy1--phthalide, 7-[ (4, 6-dimethoxy-l.3.5-triazin-2-yl)thio]-3-methyl- -phthalide, 7- [ ( 4-methoxy-6-me hyl-l , 3,5-triazin-2-yl)oxy]-3--methyl-phthalide. 3 -e hyl -7- [ ( 4 , 6-dimethoxy-l .3.5-triazi -2-yl)o y]--phthalide, 8- [ ( 4.6-dimethoxy-pyr imidin-2-yl )oxy]-3.4-dimethyl-- isochroman-2-one , 7- [ (4 , 6-dimethoxy-pyr imid in- 2 -yl )oxy]-3-methylthio--phthalide, 7- [ (4 , 6-dimethoxy-pyr imid in- 2 -yl ) oxy ] -3-vinyl- -phthalide, and 3-cyano-7-[ (4.6-d ime thoxy-pyr imid in- 2 -y1 ) oxy ] --phthalide .

14. A compound according to claim 1, selected from the group 7- [ ( 4 , 6-dimethoxy-pyr imidin-2-yl ) oxy ] -3 ,6-dimethyl--phthalide , 3-ca bamoy 1-7- [ (4.6-d ime thoxy-pyr imid in- 2 -yl ) oxy ] - -phthalide , 3-(2-chloroethoxy)-7-[(4,6-d ime thoxy-pyr imidi -2-yl)-oxy] -phthalide , 7- [ (4 , 6-dimethoxy-py imid in-2-yl ) oxy ] -3-propargyloxy--phthalide, 7- [ ( 4 , 6-dimethoxy-pyr iraidin-2-yl)oxy]-3-(n-propoxy)--phthalide , 7- [ ( 4 , 6-dimet oxy-pyr imid in- 2 -yl ) oxy ] -3- ( 2-methoxy-ethoxy) -phthalide, 7-[ (4-methoxy-pyrimidin-2-yl)oxy]-3-methyl-phthalide, 7- [ ( 4 -chl or o-6 -me thoxy-pyr imid in- 2 -yl ) oxy ] -3-methoxy--phthal ide , - 87 - 7-[ (4-dimethylamino-6-methoxy-l, 3 , 5-triazin-2-yl)oxy]--3-methyl-phthalide , 7-[ (4-methoxy-6-met ylamino-l , 3 , 5- tr iaz in-2-yl ) oxyJ -3--met yl-pht alide , 7-[(4-chloro-6-methylamino-l,3, 5-triazin-2-yl)oxy]-3- -methyl- h alide, 7-[ (4.6-dimethoxy-pyrimidin-2-yl)oxy]-3-hydroxy--p thalide , 3-cyanomethoxy-7- [ ( 4.6-dimethoxy-pyr imid in-2-yl ) oxy] --phthalide, 7- [ ( 4 , 6-dimethoxy-pyr imid in-2-yl ) oxy ] -3- (methoxy-car bony1methoxy) -phthai ide , 3-ethoxycarbonylmethyl-7- [ (4 , 6-dimethoxy-pyr imidin-2--yl) oxyJ -phthalide, 7-[ (4.6-dimethoxy-pyr imid in-2-yl) ox ]-3-methyl-2-benzo-thiophen-1 ( 3H) -one , 7- [ ( 4.6-dimethoxy-pyr imid in-2-yl )oxy]-3-methyl-iso-benzofuran-1 (3H) - thione , 7-[ (4, 6-dimethoxy-l.3.5-triazin-2-yl)oxy]-3-methyl-- isobenzofuran-1 ( 3H) -thione . 7- [ (4-dif luo omethoxy-6-methoxy-pyr imidin-2-yl ) oxy] -3-methyl-phthal ide , 8- [ (4, 6-dimethoxy-pyr imid in-2-yl) oxy] - -methy1-isochroman-l-one and 3-acetoxy-7- [ ( 4 , 6-dimethoxy-pyr imidin-2-yl ) o y ] -phthalide .

15. A weed control composition and plant growth regulating composition, which contains an effective amount of at least one compound of the general formula I - 88 - wherein W signifies one of the divalent groups a)-d) R R R I I I 4 R -c- 8 10 R R' nll 12 R R I d) - C 1 2 . . X. Y and Y each signify oxygen or sulphur, 13 Z signifies CR or nitrogen, R1 signifies hydrogen, fluorine, chlorine, C 1-3 -alkyl. halomethyl. methoxyme hyl , c 3~alkoxy, dif luoromethoxy or methylthio. 2 R signifies methyl, C1_2-alkoxy, C-^-fluoro- alkoxy, 2-alkylamino , diCC^ 2~alkyl ) amino or N-methoxymethylamino , 3 . . . R signifies hydrogen, fluorine, chlorine, bromine, optionally substituted C. -alkyl, C_ -alkenyl. 1—6 Z— 3 C2 ^-alkynyl, optionally substituted phenyl, hydroxy, optionally substituted C -alkoxy, 1— 6 C -alkylthio, phenoxy, phenylthio, cyano. 1—6 rhodano, formyl, carboxy, C -alkoxycarbonyl , 2— 5 carbamoyl, formyloxy, C -alkanoyloxy , C - 2—5 2—5 -alkoxycar bonyloxy , 3-alkylcarbamoylox , diCC^j^ 2~alkyl ) car bamoyloxy or diCC^ 2~alkoxy)- phosphonyl , 4 . . . R signifies hydrogen, C. c-alkyl or tr if luoromethyl , 5 . . . 1-6 R signifies hydrogen, C.l ^-alkyl or optionally —D substituted phenyl. 6 . . . R signifies hydrogen or methyl, - 89 - 7 8 9 R . R and R each independently signify hydrogen or C -alkyl. 10 7 . . R signifies hydrogen or C, _-alkoxy, 11 12 . R and R each independently signify hydrogen or C -alkyl. 13 7 . . R signifies hydrogen, fluorine, chlorine or methyl and 14 . . . R signifies hydrogen, halogen, C1_2~alkyl or C 2~alkoxy, as well as formulation adjuvants.

16. A composition according to claim 15 for the control of weeds.

17. A weed control composition according to claim 16, which contains an effective amount of at least one compound selected from the group 7-[ (4, 6-dimethoxy-pyrimidin-2-yl)oxy]-3-methyl--phthalide, 7- [ ( 4 , 6-dimethoxy-pyr imidin-2-yl ) oxy ] -phthalide , 3-ethyl-7-[(4, 6-dimethoxy-pyr imid in-2-yl ) oxy] --phthalide, 7-[ (4, 6-dimethoxy-py imidin-2-yl)oxy]-3-isopropyl--phthalide, 7- [ (4 , 6-dimethoxy-pyr imidin-2-yl) oxy ] -3-me thoxy--phthalide . 7- [ (4-methoxy-6-methyl-pyr imidin-2-yl) ox ] - 3 -methy1--phthalide , 7-[ (4 , 6-dimethoxy-l , 3 , 5-tr iaz in-2-yl ) oxy] -3-methyl- -phthalide, (Z)-3-ethylidene-7-[(4, 6-dimethoxy-pyr imid in-2-yl ) oxy ] -phthalide , 8- [ ( , 6-dimethoxy-pyr imid in-2-yl) oxy] -3-me thy1-iso-chroman-l-one , 7- [ (4 , 6-dimethoxy-pyr imid in-2-yl ) hio ] -3-me thy1--phthalide, - 90 - 3-ethoxy-7- [ (4.6-d imethoxy-pyr imidin-2-yl )oxy]--pht alide, 7- [ ( 4 , 6-diraethoxy-pyr imid in-2-yl ) oxy ] -3-methoxy-3--methyl-phthalide . 7-[ (4-chloro-6-methoxy-pyrimidin-2-yl)oxy]-3-methyl- -phthalide. 7- [ ( 4-ethoxy-6-methoxy-pyr imidin-2-yl) oxy] -3 -methy1--phthalide, 7- [ ( , 6-dimethoxy-l.3,5-triazin-2-yl)thio]-3-methyl--phthalide, 7-[ (4-methoxy-6-methyl-l, 3.5-triazin-2-yl)oxy]-3--methyl- phthalide , 3-ethyl-7-[ (4.6-dimethoxy-l .3.5- tr iaz in-2-y1 ) oxy] --phthalide , 8- [ ( 4.6-d imethoxy-pyr imidin-2-yl)oxy]-3,4-dimethyl- -isochroman-2-one , 7- [ (4 , 6-d imethoxy-py imid in-2-yl ) oxy] -3 -methyIthio--phthalide, 7- [ ( 4.6-diraethoxy-pyr imidin-2-yl)oxy]-3-vinyl--phthalide, and 3-cyano-7-[ (4.6-dimethoxy-pyrimidin-2-yl)oxy]--phthalide, as well as formulation adjuvants.

18. A weed control composition and plant growth *· regulating composition according to claim 15, which contains an effective amount of at least one compound selected from the group · 7- [ ( , 6-d imethoxy-pyr imidin-2-yl)oxy]-3.6-dimethyl- -phthalide , 3 -car bamo l-7- [ (4 , 6-diraethoxy-pyr imid in-2-yl ) oxy ] --phthalide, 3-(2-chloroethoxy)-7-[(4.6-d imethoxy-py imid in-2-yl ) -ox ] -phthalide , 7- [ (4 , 6-dimethoxy-pyr imidin-2-yl ) oxy ] -3-propargyloxy--phthalide , - 91 - 7-[ (4 , 6-dimethoxy-pyr imidin-2-yl )oxy]-3- (n-propoxy) - -pht alide, 7- [ (4.6-dimethoxy-pyr imid in-2-yl ) oxy] -3- ( 2-methoxy- ethoxy) -phthalide . 5 7-[ (4-methoxy-pyriraidin-2-yl)oxy]-3-methyl-phthalide. 7- [ (4-chloro-6-methoxy-pyr imidin-2-yl ) ox ] -3-methoxy- -phthal ide . 7- [ (4-dimethylamino-6-methoxy-l.3,5-triazin-2-yl)oxy]- -3-methyl-pht al ide , 10 7- [ ( 4-methoxy-6-methylamino-l , 3.5-triazin-2-yl) oxy ] -3- -methy1-phthalide , 7-[(4-chloro-6-methylamino-1.3,5-triazin-2-yl)oxy]-3- -methyl-pht alide , 7- [ ( 4.6-dimethoxy-pyr imid in-2-yl ) oxyJ -3-hydroxy-■15 -phthalide, 3-Cyanomethoxy-7- [ ( 4 , 6-dimethoxy-pyr imidin-2-yl)oxy]- -phthalide, 7- [ (4 , 6-dimethoxy-pyr imid in-2-yl ) oxy ] -3- (methoxy- car bonylmethoxy) -phthalide , 20 3-ethoxycarbonylmethyl-7- [ (4 , 6-dimethoxy-pyr imid in-2- -yl ) oxy ] -phthal ide . 7- [ (4 , 6-dimethoxy-pyr imid in-2-yl ) oxy] -3-methyl-2-benzo- thiophen-1 ( 3H) -one , 7- [ ( 4 , 6-dimethoxy-pyr imidin-2-yl)oxy]-3-methyl-iso-25 benzofuran-1 ( 3H) - thione , 7- [ ( 4 , 6-dimethoxy-l , 3,5-triazin-2- l) oxy] -3 -methyl- iso- benzofuran-l(3H) -thione, 7- [ ( 4-dif luoromethoxy-6-methoxy-py imid in- 2 -yl ) oxy ] -3- methyl-phthalide, 0 8-[ (4, 6-dimethoxy-pyrimidin-2-yl)oxy]-4-methyl- isochroman-l-one and 3 -acetoxy-7- [ ( 4 , 6-dimethoxy-pyr imid in-2 -yl ) oxy] - phthalide , as well as formulation adjuvants. 5

19. A process for the manufacture of compounds of the general formula - 92 - wherein W signifies one of the divalent groups 11 .12 d) C - X, and Y each signify oxygen or sulphur, . . 13 Z signifies CR or nitrogen. R signifies hydrogen, fluorine, chlorine, C 1-3 -alkyl. halomethyl , methoxymethyl , C Ί alkoxy , -3 dif luororaethoxy or methylthio. R signifies methyl, 2~alkoxy, C-^-fluoro- alkoxy, C 2-alkylamino , diCC^ 2~alkyl ) amino or N-met oxymethylamino , R signifies hydrogen, fluorine, chlorine, bromine, optionally substituted C_ .-alkyl. C_ -alkenyl, 1 — 6 Δ — i - 93 - C2 3-alkynyl, optionally substituted phenyl, hydroxy, optionally substituted C -alkoxy, 1—6 C -alkylthio. phenoxy, phenylthio, cyano, 1—6 rhodano, formyl, carboxy, C -alkoxycar bonyl , 2 — 5 carbamoyl, formyloxy, C -alkanoyloxy , C - 2—5 2—5 -alkoxycarbonyloxy , 3-alkylcarbamoyloxy , di(C -alkyl ) car bamoyloxy or di(C -alkoxy)- J- *™ c» phosphonyl, signifies hydrogen. C. ,-alkyl or trif luoromethyl X— o signifies hydrogen, C. ,-alkyl or optionally 1—0 substituted phenyl. signifies hydrogen or methyl, 8 9 . . . and R each independently signify hydrogen or C1_3-alkyl. signifies hydrogen or C -alkoxy, 12 . . . and R each independently signify hydrogen or C -alkyl. signifies hydrogen, fluorine, chlorine or methyl signifies hydrogen, halogen. C -alkyl or C 2-alkoxy, which process comprises reacting a compound of the general •formula wherein W, X. Y . Y and R have significances given above, with a compound of the general formula - 94 - wherein R . R and Z have the significances given above and L signifies a leaving group.

20. A process according to claim 19. wherein a compound of formula I is manufactured in which W signifies 3 . . . a group a) and R signifies hydrogen, fluorine. chlorine, bromine, optionally substituted C -alkyl, 1—6 C2 3~alkenyl. 3-alkynyl, optionally substituted phenyl, hydroxy. C -alkoxy, C -alkylthio, phenoxy, 1—6 1—6 . phenylthio, cyano or C„ c-alkoxycarbonyl and R 2-5 3 . . . signifies hydrogen or C1_6-alkyl or R signifies hydrogen, fluorine, chlorine, bromine, C -alkyl, 1—6 hydroxy, C, -alkoxy. C -alkylthio, phenoxy, phenyl- 1-6 1-6 thio or cyano and R signifies tr if luoromethyl ; or W 5 6 7 signifies a group b). c) or d) in which R , R . R . R8. R9, R10. R11 and R12 have the significances . . 1 2 given in claim 19; and X signifies oxygen, Y , Y and Z have the significances given in claim 19 and R signifies fluorine, chlorine, C -alkyl, f luoromethyl . methoxymethyl , C -alkoxy. dif luoromethoxy or methyl- 2 .1-3 thio. R signifies methyl, C -alkoxy or C - 14 . . . -f luoroalkoxy and R signifies hydrogen.

21. A method for the control of weeds and for the regulation of plant growth, which method comprises treating the locus to be protected against weeds and/or the weeds or the plants with an effective amount of a compound in accordance with any one of claims 1, 3 to 6, - 95 - 95937/2 10. 11 and 14 or of a composition in accordance with claim 15, 16 or 18.

22. A method for the control of weeds, which method comprises treating the locus to be protected against weeds and/or the weeds with an effective amount of a compound in accordance with any one of claims 2, 7 to 9, 12 and 13 or of a composition in accordance with claim 17.