Substituted phthalides and heterocyclic phthalides

Abstract: Substituted phthalides and heterocyclic phthalides and derivatives thereof which are useful as herbicides.

Description: The present invention concerns substituted phthalides and heterocyclic phthalides and derivatives thereof, processes for their production, compositions containing them and their use in agriculture. More particularly, the invention concerns compounds of formula I wherein ring system A is selected from a) phenyl or naphthyl b) pyridyl which may be fused by its (b) or (c) side to benzene c) pyridyl-N-oxide or pyrazinyl-N-oxide d) pyrimidinyl e) pyrazinyl f) 3- or 4- cinnolynyl or 2-quinoxalinyl, and g) a five membered heteroaromatic ring comprising oxygen, sulphur or nitrogen as heteroatom(s) which ring may be fused to a benzene ring or may comprise nitrogen as an additional heteroatom. R is cyano, formyl, CX 1 X 2 X 3 , -C(O)R'' wherein R'' is C 1-8 alkyl, C 1- C 8 haloalkyl, C 1-8 alkoxyC 1-8 alkyl,C 2-8 alkenyl, C 2-8 alkynyl, aryl or arylC 1-8 alkyl; a carboxyl group which may be in the form of the free acid or in ester or salt form, a thiocarboxyl group which may be in the form of the free acid or in ester form, a carbamoyl group, or a group -CONR 7 R 8 , hydroxyC 1-8 alkyl, hydroxybenzyl, -CH=NOH, -CH=NO-C 1-8 alkyl, or a ring C Y 1 , Y 2 and Y 3 are attached to carbon atoms and are independently hydrogen, halogen, hydroxy, C 1-8 alkyl, C 2-8 alkenyl, C 2-8 alkynyl, C 1-8 alkoxy, C 2-8 alkenyloxy, C 2-8 alkynyloxy, C 1-8 alkylsulfonyloxy, di(C 1-8 alkyl)sulfamoyloxy, C 1-8 alkylsulfonyl, C 1-8 alkysulfinyl, di(C 1-8 alkyl)carbamoyloxy, C 1-8 alkylthio, C 2-8 alkenylthio or C 2-8 alkynylthio each of which may in turn be substituted by 1 to 6 halogen atoms; di(C 1-8 alkoxy)methyl, conjugated C 1-8 alkoxy, hydroxyC 1-8 alkyl, C 2-8 acyl, C 2-8 acyloxy, tri(C 1-8 alkyl)silyloxy, tri(C 1-8 alkyl)silyl, cyano, nitro, amino, aryl, arylC 1-8 alkyl, aryloxy, arylC 1-8 alkoxy, arylsulfonyl, arylsulfinyl, arylthio or arylC 1-8 alkylthio, each of which may be substituted by one to three substituents selected from halogen, C 1-8 alkyl, C 1-8 haloalkyl, C 1-8 alkoxy, C 1-8 haloalkoxy, nitro, cyano, C 1-8 alkylthio, C 2-8 acyl, amino a group -C(O)-R' wherein R' is hydrogen, C 1-8 alkyl, or C 1-8 alkoxy; or Y 1 and R taken together on adjacent carbon atoms form a bridge having the formula -C(S)-O-, -C(O)-O-E- or -C(O)-N(R 2 )-E- wherein E is a direct bond or a 1 to 3 membered linking group with elements selected from methylene, -N(R 2 )- and oxygen; or Y 1 and Y 2 taken together on adjacent carbon atoms form a 3- to 5-membered bridge comprised of elements selected from methylene, -CH=, -C(R 4 )=, -NH-, oxygen and -S(O) n - ; each of W 1 , W 2 , W 3 , W 4 and W 5 is independently CH, CR 3 or nitrogen; W 6 is NH, oxygen, sulfur, -CR 4 =, -CH= or -C(O)- ; Z is a 2- or 3-membered bridge comprised of elements selected from methylene, -CH=, -C(R 4 )=, -C(O)-, -NH-, -N=, oxygen and S(O) n - ; R 1 and R 3 each is independently hydrogen, halogen, C 1-8 alkyl, C 2-8 alkenyl, C 2-8 alkynyl, C 1-8 alkoxy, C 2-8 alkenyloxy, C 2-8 alkynyloxy, C 1-8 alkylthio, C 2-8 alkenylthio or C 2-8 alkynylthio, each of which may in turn be substituted by 1 to 6 halogen atoms; C 3-6 cycloalkyl, a 5- or 6-membered heterocycloC 1-8 alkoxy, aryloxy, arylC 1-8 alkoxy or arylC 1-8 alkylthio each of which may be substituted by 1 to 3 substituents selected from halogen, C 1-8 alkyl, C 1-8 haloalkyl, C 1-8 alkoxy, C 1-8 haloalkoxy, nitro, cyano, C 1-8 alkylthio, C 2-8 acyl, amino ; aminoxy, iminoxy, amido, C 1-8 alkylsulfonylmethyl, cyano, nitro; or -C(O)-Y 4 , wherein Y 4 is hydrogen, C 1-8 alkyl, C 1-8 alkoxy, hydroxy or phenyl; R 2 is hydrogen, C 1-8 alkyl, C 1-8 haloalkyl, C 1-8 alkoxyalkyl, aryl, or arylC 1-8 alkyl; R 4 is as defined for Y 1 except for hydrogen; X and Y each is independently hydrogen, hydroxy, halogen, cyano, C 1-8 alkyl, C 1-8 alkoxy, C 1-8 alkoxycarbonyl, C 1-8 alkoxycarbonyloxy, hydroxyC 1-8 alkyl, C 1-8 haloalkyl, C 2-8 acyl, C 2-8 acyloxy, carbamoyl, carbamoyloxy, C 1-8 alkylthio, C 1-8 alkylsulfinyl, C 1-8 alkylsulfonyl or C 1-8 alkylsulfonyloxy; aryl, aryloxy, arylS(O) p , arylsulphonyloxy, each of which may in turn be substituted by 1 to 3 substituents selected from halogen, C 1-8 alkyl. C 1-8 haloalkyl, C 1-8 alkoxy, C 1-8 haloalkoxy, nitro, cyano, C 1-8 alkylthio, C 2-8 acyl; amino or together represent =O, =S, =NH, =NOR 12 or =CR 13 R 14 ; or X and R together may form a bridge having the formula -C(O)-O-, -C(O)-S or -C(O)-NR 2 - wherein the carbonyl is attached to A; p is 0, 1 or 2; X 1 , X 2 and X 3 are independently hydrogen, hydroxy, C 1-8 alkoxy, C 1-8 alkylthio, hydroxyC 1-8 alkyl or hydroxybenzyl whereby at least one of X 1 , X 2 and X 3 is other than hydrogen; or X 3 is hydrogen and X 1 and X 2 together form a 4- or 5-membered bridge comprising elements selected from -O(CH 2 ) n ,-O-, -OC(O)(CH 2 ) m O- and -S(CH 2 ) n ,S-; R 7 and R 8 are each independently (a) hydrogen, halogen; (b) C 1-24 alkyl, C 2-8 alkenyl, C 2-8 alkynyl, C 1-8 alkoxy, C 1-8 alkoxyC 1-8 alkoxy, C 2-8 -alkenyloxy, C 2-8 alkynyloxy, C 1-8 alkylthio, C 2-8 alkenylthio or C 2-8 alkynylthio, each of which may in turn be substituted by 1 to 6 halogen atoms; (c) C 3-6 cycloalkyl, C 3-6 cycloalkylC 1-8 alkyl, heterocyclyl, heterocycloC 1-8 alkyl, heterocycloC 1-8 alkoxy, aryloxy, arylC 1-8 alkoxy. or arylC 1-8 alkylthio, each of which is unsubstituted or may be substituted by 1 to 3 substituents selected from (i) halogen; (ii) C 1-8 alkyl, C 1-8 alkoxy, C 1-8 haloalkoxy, C 1-8 haloalkyl, C 1-8 alkylthio, C 1-8 alkylsulfonyl, C 1-8 alkylsulfonylmethyl; and (iii) nitro, cyano, acyl, amino; (d) amino, amido, aminosulfonyl, cyano, nitro, or -(CHR 4 ') n '''-C(O)Y 4 ', wherein Y 4 ' is hydrogen, C 1-8 alkyl, C 1-8 alkoxy or hydroxy and n''' is 0, 1, 2 or 3; R 4 ' is as defined for Y 1 ; R 12 is hydrogen or C 1-8 alkyl; R 13 and R 14 are independently hydrogen, C 1-8 alkyl or halogen; m is 1 or 2; n is 0, 1 or 2; and n' is 2 or 3; with the proviso that when R is carboxyl in free ester or salt form and X and Y together are =O one of rings A and B contains a hetero atom. Herbicidal benzylpyrimidine and benzyltriazine derivatives have been described in the European patent application EP-A-0410590, published on January 30, 1991. When R is a carboxyl or thiocarboxyl group in ester form it is preferably of formula -COOR 5 or -COSR 5 wherein R 5 is alkyl, haloalkyl, alkoxyalkyl, alkenyl, haloalkenyl, alkynl, haloalkynyl, unsubstituted or substituted aryl, unsubstituted or substituted aralkyl, hydroxyalkyl, cycloalkyl, cyanoalkyl, aralkoxyalkyl; a group -N=C(R 15 )(R 16 ); a group -(CH 2 ) n'' CH(R 17 )(R 18 ); a group R 15 and R 16 are independently hydrogen or alkyl, R 17 and R 18 are independently S(O) n alkyl, COOR 9 , alkoxy, amino, substituted amino, benzyloxy, trimethylsilyl, cyano, -C(R 19 )SR 20 or additionally one thereof may be hydrogen. R 19 is hydrogen or alkyl, R 20 is alkyl or aryl, R 9 , R 10 and R 11 are independently hydrogen, alkyl, haloalkyl, alkoxyalkyl, unsubstituted or substituted aryl or unsubstituted or substituted aralkyl, n and n'' are independently zero, one or two, and X 4 is oxygen or sulfur. When R is carboxyl in salt form the salt is preferably formed with an alkali metal, alkali earth metal, optionally substituted ammonium cation, a trialkyl sulfonium cation, a trialkylsulfoxonium cation or a phosphonium cation, especially the cation of an alkali metal (e.g. the Li or Na cation) or of an earth alkali metal (e.g. the Ca or Mg cation); the ammonium cation; a substituted ammonium cation [such as a C 1-5 alkylammonium cation, a di-C 1-5 alkylammonium cation, a tri-C 1-5 alkylammonium cation, a tetra-C 1-5 ammonium cation, a (C 1-5 alkoxy-alkyl)ammonium cation, a (hydroxy-C 1-5 alkyl)ammonium cation]; a phosphonium cation; a tri(C 1-8 akyl)sulfonium cation; or a tri(C 1-8 alkyl)sulfoxonium cation. When Y 1 , Y 2 and/or Y 3 is a carboxyl group this may be in ester or salt form or in amide form (i.e. a carbamoyl) and as such is as described above for R in these forms. Where A has meaning g) it contains one to three heteroatoms and signifies for example thienyl, furanyl, pyrrolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl or thiadiozalyl. Where A has one of the above defined heteroaromatic significances, b) through g), the substituted hetero ring is particularly selected from pyridyl, quinolyl, pyridyl-N-oxide, pyrimidinyl, pyrazinyl, thienyl or furyl, more particularly from pyridyl or thienyl. Alkyl moieties unless otherwise specified contain 1 to 8 carbon atoms, preferably 1 to 5, especially 1 to 4, e.g. 1 or 2 carbon atoms. Lower alkyl moieties contain 1 to 4, e.g. 1 or 2 carbon atoms. Alkyl moieties as present in R 5 , R 7 or R 8 contain preferably 1 to 12, especially 1 to 6 whereby one of R 7 and R 8 is preferably hydrogen when the other is alkyl. Alkyl moieties as bridging groups may be straight chain or branched and preferably contain 1 to 4, e.g. 1 or 2 carbon atoms. They may be optionally substituted by aryl or substituted aryl and may optionally be interrupted by or attached via an oxygen or sulfur atom. "Conjugated alkoxy" stands for an alkoxy group interrupted in its alkyl moiety by one or more oxygen atoms eg alkoxyalkoxy, alkoxyalkoxyalkoxy, etc. Alkenyl and alkynyl moieties contain 2 to 8, preferably 2 to 4, especially 2 or 3 carbon atoms. Halogen is preferably F, Cl or Br, especially for Cl. Aryl moieties are preferably as defined for meanings a) of ring system A, especially phenyl. Substituted amino, -amido, -aminoxy, -aminoalkyl, - iminoxy, -carbamyl (other than as R) is preferably substituted by one or two substituents selected from alkyl, alkoxy, haloalkyl, acyl, alkoxyalkyl, unsubstituted or substituted aryl or unsubstituted or substituted aralkyl. Acyl as or as part of a substituent is conveniently wherein R''' is as defined for Y 1 (for example alkyl, haloalkyl, cycloalkyl, alkoxyalkyl, unsubstituted or substituted aryl (especially phenyl). Examples of acyl include acetyl, propionyl, butyryl, unsubstituted or substituted benzoyl, pivaloyl or chloracetyl, especially acetyl or unsubstituted or substituted benzoyl. Cycloalkyl is preferably of 3 to 6 carbon atoms especially cyclopropyl, cyclopentyl or cyclohexyl. heterocyclo is preferably 5 or 6 membered and as defined for A definitions b) to g) and preferences or saturated and containing O, S or N as heteroatom, eg tetrahydrofuryl, piperidinyl, morpholinyl. For convenience bridging members such as are so written but are to be understood as embracing Carbamoyl or substituted carbamoyl moieties are attached to the molecule which they substitute via their carbonyl. Amido or substituted amido moieties are attached to the molecule which they substitute via their nitrogen atom. A particular group of compounds of formula I (compounds Ia) comprises those wherein ring system A is selected from phenyl, pyridyl or pyridyl-N-oxide. R is a carboxyl group which may be in the form of the free acid or in ester or salt form, a thiocarboxyl group which may be in the form of the free acid or in ester form, a carbamoyl group or a mono- or di- substituted carbamoyl group. Y 1 , Y 2 and Y 3 are attached to carbon atoms and are independently hydrogen, halogen, C 1-8 alkyl, C 1-8 alkoxy; each of W 1 , W 2 , W 3 and W 4 is independently CH, CR 3 or nitrogen; R 1 and R 3 each is independently hydrogen, halogen, C 1-8 alkyl, C 1-8 alkoxy, aryloxy or arylC 1-8 alkoxy. X and Y each is independently hydrogen, hydroxy, cyano. C 1-8 alkoxy, C 2-8 acyloxy or together represent =O; or X and R together form a bridge having the formula wherein the carbonyl is attached to A. When R is carboxyl or thiocarboxyl in ester form it is preferably of formula -COOR 5 or COSR 5 ; wherein each R 5 is independently alkyl, alkoxyalkyl, alkenyl, alkynyl, substituted aryl or unsubstituted or substituted aralkyl. When R is carboxy or thiocarboxyl in salt form the salt is preferably formed with an alkali metal, alkali earth metal, optionally substituted ammonium cation especially the cation of an alkali metal (e.g. the Li or Na cation) or of an earth alkali metal (e.g. the Ca or Mg cation); the ammonium cation; a substituted ammonium cation [such as a C 1-5 alkylammonium cation, a di-C 1-5 alkylammonium cation, a tri-C 1-5 alkylammonium cation, a tetra-C 1-5 ammonium cation. When R is carbamoyl or mono- or di- substituted carbamoyl it is preferably of formula CONR 7 R 8 wherein R 7 is hydrogen, alkyl, haloalkyl, alkoxyalkyl, unsubstituted oil substituted aryl or unsubstituted or substituted aralkyl and R 8 is hydrogen, alkyl, NH 2 , NHR 6 or OR 6 wherein R 6 is as defined for R 7 . A particular compound group (compounds Ib) comprises those compounds of formula I wherein ring system A represents phenyl, pyridyl or thienyl; B represents pyrimidinyl or triazinyl; R represents a ring C especially oxazole, oxazolone, oxazolidine or oxazolidinone; carboxyl in the form of the free acid or in ester or salt form; -CONR 7 R 8 , cyano or together with X represent Y 1 , Y 2 and Y 3 each represent independently hydrogen, halogen, C 1-8 alkyl, C 1-8 alkoxy, C 1-8 alkylthio or arylthio. X, Y each represent independently hydrogen, hydroxy, C 1-8 alkoxy, C 1-8 acyloxy, a ring B, halogen, C 1-8 alkylthio or arylthio or together =O or =NH and R 1 and R 3 each represent independently halogen, C 1-8 alkoxy, C 1-8 alkyl, C 1-8 haloalkoxy, aryloxy, arylC 1-8 alkoxy, C 2-8 alkylnyloxy, C 2-8 alkenyloxy. A further compound group comprises compounds Ib wherein Y 1 , Y 2 and Y 3 additionally may each represent independently aryl-C 1-8 alkoxy, C 2-8 alkenyloxy or C 2-8 alkynyloxy. B is especially pyrimidinyl, particularly 4,6-dimethoxy-2-pyrimidinyl. A is especially phenyl or pyridyl substituted as defined above. X and Y are preferably hydrogen, halogen, cyano, hydroxy, alkoxy or together =O, especially hydrogen, hydroxy or together =O. A further group of compounds according to the invention (Compounds Ic) comprises those of formula I wherein ring system A is pyridyl, R is CONR 7 'R 8 ' wherein R 7 ' and R 8 ' represent independently hydrogen, alkoxy, alkyl; or aryl or aralkyl each of which may be unsubstituted or substituted, X is hydrogen, Y is OR 3 ', SR 3 ' on OCOR 3 ' wherein R 3 ' is alkyl; or aryl; or aralkyl each of which may be unsubstituted or substituted, or X and Y together represent =O or =S and ring system B is m-CF 3 phenyl. Within this group Ic, compounds are preferred wherein X is OH and Y is H or X and Y together represent =O, A is 2- or 3-pyridyl, R 7 is hydrogen or alkyl especially methyl, R 8 is phenyl or benzoyl which may be unsubstituted or substituted eg 1-3 times by halogen, alkyl and/or alkoxy. The following meanings are preferred independently for each substituent. A a) meanings a) and b) b) phenyl c) pyridyl R a) carboxyl in the form of the free acid or in salt or ester form or carbamoyl or mono- or di-substituted carbamoyl b) COOR 5 wherein R 5 is hydrogen alkyl, COO + Ma - wherein Ma is an alkali metal cation or CONR 7 R 8 wherein R 7 is hydrogen or alkyl and R 8 is alkyl, aryl or substituted aryl c) COO - Na + , COOCH 3 , CONHC 6 H 13 , CONH(CH 3 ) phenyl Y 1 a) hydrogen, halogen, alkyl or alkoxy b) halogen, especially fluorine or chlorine Y 2 , Y 3 a) hydrogen or halogen, alkyl or alkoxy b) hydrogen or halogen c) hydrogen W 1 N W 2 a) CH or N b) CH W 3 CR 3 W 4 N W 5 a) CH or N b) N W 6 a) O b) NH Z a) elements selected from methylene, substituted methylene, b) X 1 , X 2 a) alkoxy, especially methoxy b) hydroxy X 3 a) hydrogen b) alkoxy especially methoxy R 1 , R 3 a) alkoxy, especially methoxy R 4 a) halogen, especially chlorine b) alkyl, especially methyl R 2 a) alkyl, especially methyl b) hydrogen R 5 a) alkyl, alkenyl or alkynyl b) C 1-4 alkyl, especially methyl or ethyl c) C 2-4 alkenyl d) C 2-4 alkynyl, especially propargyl R 6 , R 7 a) alkyl b) methyl, ethyl R 8 a) hydrogen b) alkyl, especially methyl or ethyl c) an aryl, especially a phenyl R 9 , R 10 , a) hydrogen or alkyl R 12 , R 15 , R 19 b) hydrogen or methyl R 11 a) alkyl b) propyl (n- or iso-) Y 4 a) alkyl or alkoxy b) CH 3 or CH 3 O R 13 , R 14 a) hydrogen or halogen b) hydrogen or fluorine R 16 a) alkyl b) C 1-4 alkyl, especially methyl or ethyl R 17 a) S(O) n alkyl or COOR 9 b) SO 2 CH 3 or COOCH 3 R 18 a) hydrogen R 20 a) alkyl or phenyl b) methyl or phenyl n a) 2 b) 0 n' a) 2 b) 3 n'' a) 1 b) 0 m a) 1 b) 2 X a) hydroxyl b) hydrogen c) taken with Y, =O d) acyloxy e) alkoxycarbonyloxy f) carbamoyloxy g) sulphonyloxy Y a) taken with X, =O b) hydrogen X + R R' a) alkyl b) alkoxy R'' a) alkyl b) methyl R''' a) alkyl b) aryl, especially phenyl Ring A, Ring B a) at least one contains a heteroatom b) ring A = a phenyl or a pyridine ring B = a pyrimidine especially 3,5 dimethoxy pyrimidine Combinations of the above listed preferred meanings are especially preferred. One such combination comprises compounds of formula (I) in which A is phenyl or pyridyl; R is a carboxyl group in the form of a free acid or salt; carbamoyl; COOR 5 '' wherein R 5 '' is C 1-5 alkyl or C 2-5 alkenyl or CONR 7 ''R 8 '' wherein R 7 '' is C 1-12 alkyl, amino, C 1-4 alkylamino, anilino, haloanilino, benzyl, halobenzyl, C 1-4 alkylbenzyl, C 1-4 alkoxybenzyl, phenyl, halophenyl, C 1-4 alkylphenyl or C 1-4 alkoxyphenyl; R 8 '' is hydrogen or C 1-4 alkyl; Y 1 , Y 2 and Y 3 are independently hydrogen or halogen; W 1 and W 4 are N; W 2 is CH; W 3 is CR 3 wherein R 3 is C 1-5 alkoxy: R 1 is C 1-5 alkoxy; X is hydroxyl or C 1-4 alkoxycarbonyloxy or taken with Y is =O; Y is hydrogen or taken with Y is =O; or X and R together form a bridge having the formula -C(O)O- wherein the carbonyl is attached to A, and Y is hydrogen or C 2-8 acyloxy. Examples of preferred compounds according to the invention are compound nos. 13, 40, 53, 55, 58, 64, 77, 78, 82, 91, 111, 124, 125, 130, 143, 149, 163, 170, 175, 199, 204, 205, 247, 249, 258, 262, 263, 265, 266, 267 and 277. Compounds having the formula especially those wherein X is CN may exist in the alternate tautomeric form The compounds of formula I according to the invention may be prepared as follows. a) when X and R combine to form a bridging group as defined above and Y is hydrogen, cyano, arylthio, arylsulfinyl or arylsulfonyl, reacting a compound of formula II wherein A is as defined above, Y' represents hydrogen, cyano, arylthio, arylsulfinyl or arylfulfonyl and Z 1 represents oxygen, sulfur or NR 2 wherein R 2 is as defined above except for hydrogen. with a compound of formula III wherein W 1 , W 2 , W 3 , W 4 are as defined above and R 21 represents methylsulfonyl, or halogen to obtain the corresponding compound of formula Ip b) treating a compound of formula Ip wherein Y' represents cyano or arylsulfonyl and Z 1 represents oxygen and the other symbols are as defined above. (i) by hydrolysis to give a corresponding compound of formula I wherein R and X form a bridge and Y is hydroxy or a compound of formula I wherein X and Y together form =O (ii) with an amine to give a corresponding compound of formula I wherein R is an optionally substituted carbamoyl group and X and Y together form =O (iii) with a group MOR 22 wherein M is an alkali metal and R 22 is hydrogen or alkyl, to give a corresponding compound wherein R and X form a bridge and Y is hydroxy or alkoxy c) hydrolyzing a compound of formula Ip wherein Y' represents hydrogen and Z 1 represents oxygen to give a compound of formula I wherein R is a carboxyl group optionally in salt form, X is hydrogen and Y is hydroxy d) ring opening a compound of formula Ip wherein Y' represents hydroxy and Z 1 represents oxygen to give a compound of formula I wherein R is a carboxyl group optionally in salt form and X and Y together are =O e) esterifying a compound of formula I wherein R is a carboxyl group optionally in salt form and X and Y are =O to give the corresponding compound wherein R is a carboxyl group in ester form f) halogenating a compound of formula Ip wherein Y' represent hydroxy to give a compound of formula I wherein X and R together form a bridging group and Y' is halogen g) reacting a compound of formula Ip wherein Z 1 is oxygen and Y' is halogen with a group R 2 NH 2 and a group HOR 23 wherein R 23 represents alkyl, acyl or aryl and R 2 is as defined above to give the corresponding compound wherein Z 1 is NR 2 and Y' is alkoxy, aryloxy or acyloxy h) oxidizing a compound of formula Ip wherein Y' represents hydrogen to give the corresponding compound wherein Y' represents hydroxy i) reacting a compound of formula IV with a compound of formula V to produce a compound of formula Iq wherein A, R, R 1 , W 1 , W 2 , W 3 , W 4 , Y 1 , Y 2 and Y 3 are as defined above and X'' and Y'' are hydrogen and R 24 is alkyl, especially methyl j) mono-or di-halogenating a compound of formula Iq wherein X'' and Y'' are hydrogen to produce the corresponding compound of formula Iq wherein one or both of X'' and Y'' are halogen k) oxidizing a compound of formula Iq wherein X'' and Y'' are both hydrogen or X'' is halogen and Y'' is hydrogen to produce the corresponding compound wherein X'' and Y'' together represent =O or one represents hydrogen and the other represents hydroxy l) alkylating a compound of formula Iq wherein X'' represents hydrogen and Y'' represents hydrogen to produce the corresponding compound wherein X'' represents alkyl and Y'' represents hydrogen m) introducing an alkoxy or alkylthio group into a compound of formula Iq wherein X'' represents halogen and Y'' represents hydrogen to produce the corresponding compound wherein X'' represents alkoxy or alkylthio and Y'' represents hydrogen n) acylating a compound of formula Iq wherein X'' represents hydroxy and Y represents hydrogen to produce the corresponding compound wherein X'' represents acyloxy and Y'' represents hydrogen o) reacting a compound of formula Ip wherein Z 1 is oxygen and Y' is hydrogen with a group R 7 NH 2 wherein R 7 is as defined above to give a compound of formula I wherein R is monosubstituted carbamoyl, X is hydrogen and Y is hydroxy p) sulfonylating, carbamoylating, acylating or carbalkoxylating a compound of formula Ip wherein Z 1 is oxygen and Y' is hydroxy to produce the corresponding compound of formula I wherein R and X form a bridge and Y represents sulfonyloxy, carbamoyloxy, acyloxy or alkoxycarbonoyloxy q) reacting a compound of formula Ip wherein Z 1 is oxygen and Y' is halogen with a group R 7 R 8 NH wherein R 7 and R 8 are as defined above (R 7 and R 8 ≠ H) to give a compound of formula I wherein R is disubstituted carbamoyl, and X and Y together represent =O. and recovering any compound wherein R is a carboxyl or thiocarboxyl group in free form or in ester form and any compound wherein R is carboxyl in free form or in salt form. The following table is illustrative of suitable reaction conditions. Process a) through p) also form part of the invention. The starting materials of formula II or III are either known or may be prepared analogously to known methods. The compounds of formula I have herbicidal activity as observed after their pre-emergent or post-emergent application to weeds or a weed locus. The term "herbicide" (or "herbicidal") refers to an active ingredient (or an effect) which modifies the growth of plants because of plant growth regulating or phytotoxic properties so as to retard the growth of the plant or damage the plant sufficiently to kill it. Application of a compound of formula I is made according to conventional procedure to the weeds or their locus using a herbicidally effective amount of the compound, usually from 10 g to 10 kg/ha. Compounds according to the invention may be used in the control of both broad-leaf and grassy weeds on both pre- and post-emergent application. Compounds may also exhibit selectivity in various crops and are thus suited for use in weed control in crops such as corn, cotton, wheat and soybean. The optimum usage of a compound of formula I is readily determined by one of ordinary skill in the art using routine testing such as greenhouse testing and small plot testing. It will depend on the compound employed, the desired effect (a phytotoxic effect requiring a higher rate than a plant growth regulating effect), the conditions of treatment and the like. In general satisfactory phytotoxic effects are obtained when the compound of formula I is applied at a rate in the range of from 0.01 to 5.0 kg, more preferably of from 0.05 to 2.5 kg per hectare, eg 0.05 to 5.0 kg per hectare, especially 0.1 to 2.5 kg kper hectare. The compounds of formula I may be advantageously combined with other herbicides for broadspectrum weed control. Examples of herbicides which can be combined with a compound of the present invention include those selected from the carbamates, thiocarbamates, chloroacetamides, dinitroanilines, benzoic acids, glycerol ethers, pyridazinones, semicarbazones, uracils and ureas for controlling a broad spectrum of weeds. The compounds of formula I are conveniently employed as herbicidal compositions in association with agriculturally acceptable diluents. Such compositions also form part of the present invention. They may contain, aside from a compound of formula I as active agent, other active agents, such as herbicides or compounds having antidotal, fungicidal, insecticidal or insect attractant activity. They may be employed in either solid or liquid forms eg in the form of a wettable powder or an emulsifiable concentrate incorporating conventional diluents. Such compositions may be produced in conventional manner, eg by mixing the active ingredient with a diluent and optionally other formulating ingredients such as surfactants. Agriculturally acceptable additives may be employed in herbicidal compositions to improve the performance of the active ingredient and to reduce foaming, caking and corrosion, for example. The term "diluent" as used herein means any liquid or solid agriculturally acceptable material which may be added to the active constituent to bring it in an easier or improved applicable form, respectively, to a usable or desirable strength of activity. It can for example be talc, kaolin, diatomaceous earth, xylene or water. "Surfactant" as used herein means an agriculturally acceptable material which imparts emulsifiability, spreading, wetting, dispersibility or other surface-modifying properties. Examples of surfactants are sodium lignin sulfonate and lauryl sulfate. Particularly formulations to be applied in spraying forms such as water dispersible concentrates or wettable powders may contain surfactants such as wetting and dispersing agents, for example the condensation product of formaldehyde with naphthylene sulphonate, an ethoxylated alkylphenol and an ethoxylated fatty alcohol. In general, the formulations include from 0.01 to 90% by weight of active agent and from 0 to 20% by weight of agriculturally acceptable surfactant, the active agent consisting either of at least one compound of formula I or mixtures thereof with other active agents. Concentrate forms of compositions generally contain between about 2 and 90%, preferably between about 5 and 70% by weight of active agent. Application forms of formulation may for example contain from 0.01 to 20% by weight of active agent. Typical herbicidal compositions, according to this invention, are illustrated by the following Examples A, B and C in which the quantities are in parts by weight. EXAMPLE A Preparation of a Dust 10 Parts of a compound according to this invention and 90 parts of powdered talc are mixed in a mechanical grinder-blender and are ground until a homogeneous, free-flowing dust of the desired particle size is obtained. This dust is suitable for direct application to the site of the weed infestation. EXAMPLE B Preparation of a Wettable Powder 25 Parts of a compound according to this invention are mixed and milled with 25 parts of synthetic fine silica, 2 parts of sodium lauryl sulphate, 3 parts of sodium ligninsulphonate and 45 parts of finely divided kaolin until the mean particle size is about 5 micron. The resulting wettable powder is diluted with water before use to a spray liquor with the desired concentration. EXAMPLE C Preparation of Emulsifiable Concentrate (EC) 13.37 Parts of a compound according to this invention are mixed in a beaker with 1.43 parts of Toximul 360A (a mixture of anionic and nonionic surfactants containing largely anionic surfactants), 5.61 parts of Toximul 360A (a mixture of anionic and non-ionic surfactants containing largely non-ionic surfactants), 23.79 parts of dimethylformamide and 55.8 parts of Tenneco 500-100 (predominantly a mixture of alkylated aromatics such as xylene and ethylbenzene) until solution is effected. The resulting EC is diluted with water for use. The following examples are provided to illustrate the practice of the present invention. Temperature is given in degrees Celsius. Abbreviations used in this specification. THF = tetrahydrofuran LDA = lithiumdiisopropylamide RT = room temperature DMF = dimethylformamide DDQ = 2,3-dichloro-5,6-dicyanobenzoquinone NBS = N-bromosuccinimide DMSO = Dimethylsulfoxide MEK = Methylethylketone DMAP = Dimethylaminopyridine Individual alkyl substituents listed in the following tables from A to F are in the "n" isomeric form unless otherwise indicated. EXAMPLE 1 7-chloro-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide (Table A, cpd. no. 6) 1.68 g (0.01 mol) of 7-chlorophthalide is added to 100 ml of dry THF and the mixture cooled to -70°C. 6.8 ml (0.01 mol) of 1.5 M LDA is then added over 3 minutes and the reaction mixture stirred at -70°C for 15 minutes. 2.18 g (0.01 mol) of 2-methylsulfonyl-4,6-dimethoxypyrimidine in 50 ml of THF is then added and the mixture stirred for 4 hrs with temperature being maintained at -75 to -70°C. The reaction mixture is neutralized with 1.5 g of NH 4 Cl in 5 ml of water, warmed and concentrated on a rotovaporator. The concentrate is partitioned between CH 2 Cl 2 /H 2 O (50 ml each) and the aqueous phase separated and treated with further 30 ml of CH 2 Cl 2 . The combined CH 2 Cl 2 phases are washed with 30 ml of water, separated and concentrated. The concentrate was flash chromatographed on silica gel using 80/20 hexane/ethyl acetate (500 ml), 50/50 hexane/ethyl acetate (500 ml) and 80/20 acetone/methanol (500 ml) (30 fractions X 50 ml). The title compound (fractions 9-23) was obtained after recrystalization from hexane/CH 2 Cl 2 as a white solid, m.p. 148-149°C. EXAMPLE 2 5-(4,6-dimethoxy-2-pyrimidinyl)-furo[3,4,b] pyridine-7(5H)-one (Table B, cpd. no. 40) A solution of 1.3 g (0.0096 mols) of furo [3,4-b]pyridine-7(5H)-one in 50 ml of dry THF is cooled to -75° C and 8 ml (0.0192 mols) of 2.5 M LDA added dropwise over 5 minutes. The mixture is allowed to react for 1 hr at -75° C and 2.1 g (0.0096 mol) of 2-methylsulfonyl-4,6-dimethoxypyrimidine in 30 ml of dry THF added dropwise over 10 minutes. The mixture is allowed to warm to RT, 1.6 ml of HCl added and the THF evaporated off. The residue is dissolved in 75 ml of CH 2 Cl 2 , washed with water (2 x 50 ml) and the organic phase concentrated to give a yellowish white gummy solid. This is chromatographed on a silica gel column using 50/50 hexane/ethylacetate (500 ml), ethyl acetate (500 ml) and 80/20 acetone/methanol (1000 ml) (30 fractions). The crystalline residue (fractions 18-21) of the title product has m.p. of 167-168°C. EXAMPLE 3 7-chloro-3-methoxy-3-(4,6-dimethoxy-2-pyrimidinyl)-2-methylisoindol-1(3H)-one (Table C, cpd. no. 54) A mixture of 0.5 g of 7-chloro-3-hydroxy-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide, 30 ml of CCl 4 , 2 ml of SOCl 2 and 4 drops of DMF is heated at 65°C for 1½ hrs, cooled and excess SOCl 2 and CCl 4 removed on a rotovaporator. The residue is diluted with 20 ml of CH 2 Cl 2 and added to a mixture of 5 ml of 40% aq methylamine and 10 ml of methanol with stirring over ½ hr. The mixture is placed on a rotovaporator and the residue partitioned between 50 ml each of CH 2 Cl 2 and water. The organic phase is concentrated and flash chromatographed on silica gel using 50/50 hexane/ethyl acetate (800 ml), ethyl acetate (500 ml) and 80/20 acetone/methanol (200 ml) (30 fractions X 50 ml). The product (fractions 19-21) was obtained as a yellow gum. EXAMPLE 4 7-chloro-3-hydroxy-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide (Table A, cpd. no. 13) A mixture of 1.8 g of 7-chloro-3-cyano-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide, 50 ml of 1% NaOH and 50 ml of THF are stirred at room temperature for 3 hrs. The THF is removed by evaporation and the mixture is diluted with water and extracted twice with ethyl acetate. The aqueous solution is acidified with 2N-H 2 SO 4 . The resulting acid solution is extracted with 3 x 100 ml ethyl acetate and the organic phases combined, dried over Na 2 SO 4 and concentrated to give a pale yellow solid. This residue is taken up in ethyl acetate and treated with activated charcoal until the yellow base line material is removed to give the title product as a white solid m.p. 188-190°C. EXAMPLE 5 7-chloro-3-methoxy-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide (Table A, cpd. no. 30) 1.0 g of 7-chloro-3-cyano-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide is slurried in 20 ml of methanol and the solution cooled with ice and 0.6 ml of sodium methoxide added dropwise. After stirring for 10 min a further 1 ml of sodium methoxide is added and stirring continued for 10 min and the mixture is then quenched with 2N H 2 SO 4 . Methanol is removed on a rotovaporator and the residue partitioned between water and ethyl acetate. The organic phase is dried over Na 2 SO 4 and concentrated. Flash chromatography of the residue over silica gel using 25% ethyl acetate/hexane yields a white solid m.p. 180-183°C. EXAMPLE 6 a) Methyl 2-chloro-6-(4,6-dimethoxy-2-pyrimidinylcarbonyl)benzoate (Table C, cpd. no. 55), and b) 7-chloro-3-chloro-(4,6-dimethoxy-2-pyrimidinyl)phthalide (Table A, cpd. no. 21) A mixture of 0.7 g of 7-chloro-3-hydroxy-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide, 30 ml of CCl 4 , 2 ml of SOCl 2 and 4 drops of DMF are refluxed at 60° for 1½ hrs. The mixture is then cooled, excess SOCl 2 and CCl 4 removed on a rotovaporator. The residue is diluted with 20 ml of CH 2 Cl 2 and added to a stirred mixture of 10 ml of methanol and 2 ml of diethylamine. After 2½ hrs the mixture is stripped on a rotovaporator to remove excess CH 2 Cl 2 and methanol and the residue partitioned between CH 2 Cl 2 (50 ml) and water (50 ml). The organic phase is separated, concentrated and the gummy residue flash chromatographed over silica gel using 80/20 hexane/ethyl acetate (500 ml), 60/40 hexane/ethyl acetate (500 ml) (28 fractions X 50 ml). Fractions 18 to 20 yielded title compound a) and fractions 11 to 16 the compound b). EXAMPLE 7 7-chloro-3-cyano-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide (Table A, cpd. no. 27) 600 mg of 7-chloro-3-cyanophthalide are added to an ice-cold suspension of hexane washed 60% NaH (160 mg) in DMF (20 ml). After 15 min, 710 mg of 2-methylsulfonyl-4,6-dimethoxypyrimidine are added. After stirring at RT for 1½ hr the mixture is poured onto 200 ml of ice/water acidified with 2N H 2 SO 4 and stirred. The precipitate is filtered and dried in a vacuum oven to yield the title product, m.p. 159-161°C. EXAMPLE 8 7-chloro-3,3-bis(4,6-dimethoxy-1,3,5-triazin-2-yl)phthalide (Table A, cpd. no. 36) 1.48 g of 7-chlorophthalide are dissolved in 80 ml of THF. The solution is cooled to -70°C and 1.5 M LDA in THF (6 ml) is syringed in at -70°C over 3 min. Stirring is continued for 15 min at -70°, 1.54 g of 2-chloro-4,6-dimethoxy-1,3,5-triazine in 50 ml of THF added dropwise and the mixture is then allowed to warm to -20°. The mixture is again cooled to -70° and 1 ml of conc. HCl in 10 ml of water is added. The mixture is stirred for 25 min and allowed to warm to RT and the THF is removed by evaporation. The residue is partitioned between CH 2 Cl 2 and water (50 ml each) and the aqueous phase extracted with an additional 30 ml of CH 2 Cl 2 . The combined organic phases are washed with 30 ml of water and concentrated to give a yellow gum. This is flash chromatographed on silica gel using 60/40 hexane/ethyl acetate (1000 ml), ethyl acetate (400 ml), 80/20 acetone/ methanol (500 ml) (30 fractions X 50 ml, 1 X 200 ml). Fractions 21 and 22 yielded a yellow gum which upon recrystalization from hexane yielded title product m.p. 126-127° as a yellow solid. EXAMPLE 9 Lithium 2-chloro-6-(4,6-dimethoxy-α-hydroxy-2-pyrimidinylmethyl)benzoate (Table C, cpd. no. 53) A mixture of 1.0 g of 7-chloro-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide, 0.136 g of LiOH.H 2 O, 2 ml of water and 10 ml of methanol is stirred overnight at RT. The mixture is evaporated to dryness on a rotovaporator. Further drying in a drying pistol yield the title compound as a white solid, m.p. 153-157°C. EXAMPLE 10 Lithium 3-[(4,6-dimethoxy-α-hydroxy-2-pyrimidinyl)methyl]pyridine-2-carboxylate (Table D, cpd. no. 64) A mixture of 0.490 g of 5-(4,6-dimethoxy-2-pyrimidinyl)furo [3,4,b]pyridine-7(5H)-one, 0.0768 gm of LiOH.H 2 O, 10 ml of methanol and 2 ml of water is stirred for 24 hrs under nitrogen at RT and the solvent stripped off. The yellowish solid is dried for a further 2 hrs to yield the title product, m.p. >250°C (decomp.). EXAMPLE 11 Sodium 2-chloro-6-[(4,6-dimethoxy-2-pyrimidinyl)carbonyl]benzoate (Table C, cpd. no. 58) 1.24 g of 7-chloro-3-hydroxy-3-(4,6-dimethoxy-2-pyrimidinyl)phthalide, 154 mg NaOH, 25 ml THF and 25 ml water are mixed until a yellow homogenous solution is achieved. The solvents are stripped on a rotovaporator and then on a Kugelrohr at 100°C to produce the title compound as a yellow solid, m.p. 276-278°C. EXAMPLE 12 3-[(4,6-dimethoxy-2-pyrimidinyl)carbonyl]-pyridine-2-carboxylic acid (Table D, cpd. no. 63) 490 mg of 5-(4,6-dimethoxy-2-pyrimidinyl)-furo[3,4-b]pyridine-7(5H)-one is dissolved in 50 ml of methanol and the mixture heated with stirring at 50°C until a homogenous solution is formed (ca ½ hr). 2.6 g of NaOCl is added dropwise and the solution heated for a further ½ hr at 55°C. 0.208 g of 50% NaOH is added at 55° and the mixture heated for a further ½ hr at this temperature and then cooled in an ice-bath and acidified with 1 ml conc. HCl. The solvent is evaporated and the residue partitioned between 50 ml of CH 2 Cl 2 and 50 ml of water. The organic phase is concentrated to give a white solid, m.p. 71-73°. EXAMPLE 13 2-[(4,6-dimethoxy-2-pyrimidinyl)-α-iminomethyl]benzoic acid (Table C, cpd. no. 51) 2.67 g of isopropyl 2-bromobenzoate are dissolved in 100 ml of dry diethylether, the solution cooled to -100° C and 6.6 ml of 1.6 M n-butyllithium solution added. Stirring is continued for 10 min and 12 g of 2-cyano-4,6-dimethoxypyrimidine in 60 ml of diethylether is added over 2 min at -100°C. The mixture is stirred for ½ hr at -80° and then allowed to warm to RT. 3 g of NH 4 Cl in 30 ml of water is added to the reaction mixture, cooled in an ice-bath. The ether layer is separated off, washed with water (2 x 30 ml) and concentrated. The gummy residue is dissolved in 20 ml of 85/15 hexane/ethyl acetate, and CH 2 Cl 2 , and flash chromatographed on silica gel using 800 ml 85/15 hexane/ethyl acetate, 500 ml 1% methanol in ethyl acetate, 500 ml 5% methanol in ethyl acetate and 500 ml of 80/20 acetone/methanol (40 fractions at 50 ml; 1 at 200 ml). Fractions 7 to 10 yielded title compound which on recrystallization from CH 2 Cl 2 melted at 225-235°C. EXAMPLE 14 5-Chloro-5-(4,6-dimethoxy-2-pyrimidinyl)furo[3,4,b]pyridine-7(5H)-one (Table B, cpd. no. 68) A mixture of 490 mg of 5-(4,6-dimethoxy-2-pyrimidinyl)furo[3,4,b]pyridine-7(5H)one and 50 ml of methanol is heated at 55° for 1/2 hour or until a homogenous solution is formed. 2.6 g of NaOCl (common house bleach) is added dropwise. The mixture is taken up in dichloromethane an the organic phase separated and evaporated to dryness to yield the title compound. EXAMPLE 15 3-[(4,6-dimethoxy-2-pyrimidinyl)carbonyl]-pyridine-2-carboxylic acid (Table E, cpd. no. 63) 0.208 g of 50% NaOH is added at 55° to a solution of 0.551 g of 5-chloro-5-(4,6-dimethoxy-2-pyrimidinyl)-furo[3,4,b]pyridine (Table B, cpd. no. 68) in 50 ml methanol. The mixture stirred for a further 1/2 hr at 55°, cooled in an ice-bath, acidified with 1 ml of concentrated HCl and the solvent evaporated. The residue is partitioned between 50 ml of CH 2 Cl 2 and 50 ml H 2 O and the CH 2 Cl 2 layer concentrated to give 0.39 g of the title product as a white solid, m.p. 71-73°C. EXAMPLE 16 2-(2-(4,4-dimethyl-oxazolin-2-yl)-benzyl)-4,6-dichloropyrimidine (Table C, cpd. no. 61) To a mixture of 1.25 g of 2-o-tolyl-4,4-dimethyl-oxazoline in 20 ml of ether under N 2 atmosphere at -30°C is added by syringe 4.2 ml of 1.6 M n-butyllithium in hexane with stirring which is continued for 1 hr at -10°C. 0.98 g of 4,6-dichloropyrimidine in 20 ml of ether are added slowly to the reaction mixture which is then stirred at -45 to -30°C for 30 min and at 0°C for a further 30 min. The reaction mixture is quenched with acetic acid (0.4 ml) and water (0.1 ml) in THF (1.3 ml) and then treated with 1.5 g of 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) in 6 ml of THF. The temperature is brought to RT and the mixture stirred for 5 min after cooling to 0°C. 7.6 ml of 1N NaOH (cooled) are added and the mixture stirred for 5 min. The organic phase is separated and dried over Na 2 SO 4 filtered and the solvent removed. Following chromatography (10/90 ether/hexane) the title product is obtained. EXAMPLE 17 2-(2-(4,4-dimethyl-oxazolin-2-yl)-benzyl)-4,6-dimethoxypyrimidine (Table C, cpd. no. 48) To a solution of 1.7 g of 2(2-(4,4-dimethyl-oxazolin-2-yl)-benzyl)-4,6-dichloropyrimidine in 100 ml of methanol are added 2.18 g of 25% methanolic NaOCH 3 and the mixture heated for 10 hrs at 65°C with stirring. The temperature is lowered to 60° and stirring continued overnight. The solvent is stripped and the residue taken up in 80 ml of toluene and 50 ml of water. The toluene layer was separated and washed with 50 ml of water, separated and concentrated to give the title compound as a yellow oil. EXAMPLE 18 2-(2-(4,4-dimethyl-oxazolin-2-yl)-α-bromobenzyl)-4,6-dimethoxy pyrimidine (Table C, cpd. no. 62) 0.55 g of 2-(2-(4,4-dimethyl-oxazolin-2-yl)-benzyl)-4,6-dimethoxypyrimidine, 0.30 g of a N-bromosuccinimide, 0.03 g of benzoyl peroxide are dissolved in 60 ml of CCl 4 and heated under reflux overnight at 75°C. The reaction mixture is filtered and the filtrate washed with 5% NaHCO 3 solution (50 ml), 50 ml of water and the organic phase separated and concentrated to give the title compound. EXAMPLE 19 2-(2-(4,4-dimethyl-oxazolin-2-yl)-benzoyl)4,6-dimethoxypyrimidine (Table C, cpd. no. 49) A mixture of 1.2 g of 2-(2-(4,4-dimethyl-oxazolin-2-yl)-α-bromobenzyl)-4,6-dimethoxy-pyrimidine and 2 g of Na 2 CO 3 in 30 ml of DMSO is heated with stirring at 50-60°C for 3 hrs. The mixture is poured into 150 ml of water and extracted with toluene. The toluene extract is washed twice with water (2 x 50 ml) separated and concentrated. The thus obtained gum is chromatographed with 800 ml of 80/20 hexane/ethyl acetate, 500 ml 70/30 hexane/ethyl acetate, 60/40 ml hexane/ethyl acetate (50 ml fractions) fractions 29 to 34 yielded the title compound. EXAMPLE 20 2-chloro-6-(4,6-dimethoxy-2-pyrimidinylcarbonyl)-benzoic acid dimethylamide (Table C, cpd. no. 57) 1.0 g of 7-chloro-3-cyano-3-(4,6-dimethoxy-2-pyrimidinyl) phthalide is dissolved in 15 ml of THF. 0.7 ml of a 40% aqueous dimethylamine solution is then added via syringe whereupon the solution darkens. Stirring is continued at R.T. for 15 minutes and the mixture diluted with water and partitioned between ethyl acetate and water. The organic phase is separated, washed with 2N H 2 SO 4 , then brine, dried and concentrated. The residue is purified on silica gel, eluant 200 ml of 50% ethyl acetate/hexane then 100% ethyl acetate. Fractions 12 to 15 yielded the title compound, m.p. 141-142°C. EXAMPLE 21 3-acetoxy-7-chloro-3-(4,6-dimethyloxy-2-pyrimidinyl)phthalide (Table A, cpd. no. 125) 1.1gof7-chloro-3-(4,6-dimethoxy-2-pyrimidinyl)-3-hydroxy-phthalide is dissolved in 20 ml of pyridine and 0.3 ml of acetic anhydride added with stirring. After stirring for 20 min the mixture is poured into 2N HCl and extracted with two portions of ethylacetate. The combined ethyl acetate extracts are washed once with 2N HCl, once with H 2 O and once with brine and dried over magnesium sulfate. Filtration and evaporation produced the title compound as a white solid, m.p. 213-215°. EXAMPLE 22 3-[(4,6-dimethoxy-α-hydroxy-2-pyrimidinyl)methyl]pyridine-2-carboxamide (Table E, cpd. no. 82) To a solution of 0.9 g of ammonia, in 15 ml of methanol, is added 0.5 g of 3[(4,6-dimethoxy-2-pyrimidinyl)-7-azaphthalide. After stirring for 2 hrs at RT, the methanol is removed under reduced pressure and the concentrate recrystallized from toluene to give the title compound as a white solid, m.p. 135-137°C. EXAMPLE 23 3[(4,6-dimethoxy-2-hydroxy-2-pyrimidinyl)methyl]pyridine-2-[carboxy(4-isopropyl)anilide] (Table E, cpd. no. 183) To a solution of 3 ml of 4-isopropylaniline in 50 ml of toluene is syringed in 4 ml of 15.6% trimethylaluminum in hexane at RT. The mixture is stirred for 0.5 hr at RT and 0.5 g of 3-[(4,6-dimethoxy-2-pyrimidinyl)-7-azaphthalide is added. The mixture is stirred for 2 hrs at RT and acidified with 30 ml of 10% hydrochloric acid at 5-10°C. The toluene solution is separated, washed with 20 ml of 10% hydrochloric acid, 20 ml of 5% sodium carbonate and 20 ml of water, dried and concentrated. The concentrate is recrystallized from hexane to yield the title compound as a white solid, m.p. 113-114°C. TABLE 24 3-[(4,6-dimethoxy-α-(ethoxycarbonyloxy)-2-pyrimidinyl)methyl]pyridine-2-carbaxamide (Table E, cpd. no. 129) To a solution of 0.5 g of 3-[(4,6-dimethoxy-α-hydroxy-2-pyrimidinyl)methyl]pyridine-2-carboxamide, 0.05 g of 4-(dimethylamino)pyridine, and 1 ml of triethylamine, in 20 ml of toluene and 10 ml of dichloromethane is added 1 ml of ethyl chloroformate at RT. After stirring for 1 hr at ambient temperature, the mixture is washed with water (2x30 ml), dried and concentrated on a rotoevaporator. The concentrate is digested with v/v mixture of hexane-toluene, 10 ml, at 50°C, cooled to RT and filtered to isolate 0.45 g of the title compound as a yellow solid, m.p. 112-114°C. EXAMPLE 25 3-[(4,6-dimethoxy-α-benzoyloxy-2-pyrimidinyl)methyl]pyridine-2-(N,N-dibenzoyl)carboxamide (Table E, cpd. no. 159) To a solution of 0.05 g of 3-[(4,6-dimethoxy-α-hydroxy-2-pyrimidinyl)methyl]-2-carboxamide, 0.5 g, 4-(dimethylamino)pyridine and 4 ml of triethylamine in 30 ml of dichloromethane is added 1.4 g of benzoyl chloride at RT in two portions. The reaction mixture is stirred at RT for 17 hrs and washed with 30 ml of water, 30 ml of 5% hydrochloric acid and 30 ml of water. The dichloromethane solution is concentrated and the concentrate flash chromatographed through 300 ml silica gel, 230-400 mesh, using 1 L 70/30 hexane-ethyl acetic and 500 ml 50/50 hexane-ethyl acetate as eluting solvent mixtures. Fractions 18-21 gave after recrystallization from 70/30 hexane ethyl acetate the title compound as a white solid, m.p. 168-170°C. EXAMPLE 26 3-[(4,6-dimethoxy-α-(N-methylcarbamoyloxy)-2-pyrimidinyl)methyl]-2-pyridine carbox(N-allyl)amide (Table E, cpd. no. 133) To a solution of 0.5 g of 3-[(4,6-dimethoxy-α-hydroxy-2-pyrimidinyl)methyl]-2-pyridine carbox(N-allyl)amide and 3 drops of triethylamine, in 20 ml of dichloromethane is added 3 ml of methyl isocyante, in three 1 ml portion/day while stirring at RT for 3 days. The reaction mixture is washed with water (2x50ml), dried and concentrated. The concentrate is flash chromoatographed through 300 ml silica gel, 230-400 mesh, using 1 L 50/50 hexane-ethyl acetate, 500 ml ethyl acetate, 500 ml 80/20 ethyl acetate methanol taking 34 fractions (50 m/m). Fractions 21-25 give 0.4 g of the title product as a yellow gum. The following compounds may be prepared analogously to the preceding examples or as otherwise described herein. Compounds of Table F wherein COOH is replaced by other meanings of R as listed in Tables C, D and E above for R may be prepared analogously.

Claims: A compound of formula I wherein ring A is selected from a) phenyl or naphthyl b) pyridyl which may be fused by its (b) or (c) side to benzene c) pyridyl-N-oxide or pyrazinyl-N-oxide d) pyrimidinyl e) pyrazinyl f) 3- or 4-cinnolynyl or 2-quinoxalinyl, and g) a five membered heteroaromatic ring comprising oxygen, sulphur or nitrogen as heteroatom which ring may be fused to a benzene ring or may comprise nitrogen as an additional heteroatom; R is cyano, formyl, CX 1 X 2 X 3 , -C(O)R'' wherein R'' is C 1-8 alkyl, C 1- C 8 haloalkyl, C 1-8 alkoxyC 1-8 alkyl,C 2-8 alkenyl, C 2-8 alkynyl, aryl or arylC 1-8 alkyl; a carboxyl group which may be in the form of the free acid or in ester or salt form, a thiocarboxyl group which may be in the form of the free acid or in ester form, a carbamoyl group, or a group -CONR 7 R 8 , hydroxyC 1-8 alkyl, hydroxybenzyl, -CH=NOH, -CH=NO-C 1-8 alkyl, or a ring C Y 1 , Y 2 and Y 3 are attached to carbon atoms and are independently hydrogen, halogen, hydroxy, C 1-8 alkyl, C 2-8 alkenyl, C 2-8 alkynyl, C 1-8 alkoxy, C 2-8 alkenyloxy, C 2-8 alkynyloxy, C 1-8 alkylsulfonyloxy,di(C 1-8 alkyl)sulfamoyloxy,C 1-8 alkylsulf onyl, C 1-8 alkylsulfinyl, di(C 1-8 alkyl)carbamoyloxy, C 1-8 alkylthio, C 2-8 alkenylthio or C 2-8 alkynylthio each of which may in turn be substituted by 1 to 6 halogen atoms; di(C 1-8 alkoxy)methyl, conjugated C 1-8 alkoxy,hydroxyC 1-8 alkyl, C 2-8 acyl,C 2-8 acyloxy,tri(C 1-8 alkyl)silyloxy, tri(C 1-8 alkyl)silyl, cyano, nitro, amino, aryl, arylC 1-8 alkyl, aryloxy, arylC 1-8 alkoxy, arylsulfonyl, arylsulfinyl, arylthio or arylC 1-8 alkylthio, each of which may be substituted by one to three substituents selected from halogen, C 1-8 alkyl, C 1-8 haloalkyl, C 1-8 alkoxy, C 1-8 haloalkoxy, nitro, cyano, C 1-8 alkylthio, C 2-8 acyl, amino a group -C(O)-R' wherein R' is hydrogen, C 1-8 alkyl, or C 1-8 alkoxy; or Y 1 and R taken together on adjacent carbon atoms form a bridge having the formula -C(S)-O-, -C(O)-O-E- or -C(O)-N(R 2 )-E- wherein E is a direct bond or a 1 to 3 membered linking group with elements selected from methylene, -N(R 2 )- and oxygen; or Y 1 and Y 2 taken together on adjacent carbon atoms form a 3- to 5-membered bridge comprised of elements selected from methylene, -CH=, -C(R 4 )=, -NH-, oxygen and S(O) n - ; each of W 1 , W 2 , W 3 , W 4 and W 5 is independently CH, CR 3 or nitrogen; W 6 is NH, oxygen, sulfur, -CR 4 =, -CH= or -C(O)- ; Z is a 2- or 3-membered bridge comprised of elements selected from methylene, -CH=, -C(R 4 )=, -C(O)-, -NH-, -N=, oxygen and -S(O) n - ; R 1 and R 3 each is independently hydrogen, halogen, C 1-8 alkyl, C 2-8 alkenyl, C 2-8 alkynyl, C 1-8 alkoxy, C 2-8 alkenyloxy, C 2-8 alkynyloxy, C 1-8 alkylthio, C 2-8 alkenylthio or C 2-8 alkynylthio, each of which may in turn be substituted by 1 to 6 halogen atoms; C 3-6 cycloalkyl, a 5- or 6-membered heterocycloC 1-8 alkoxy, aryloxy, arylC 1-8 alkoxy or arylC 1-8 alkylthio each of which may be substituted by 1 to 3 substituents selected from halogen, C 1-8 alkyl, C 1-8 haloalkyl, C 1-8 alkoxy, C 1-8 haloalkoxy, nitro, cyano, C 1-8 alkylthio, C 2-8 acyl, amino; aminoxy, iminoxy, amido, C 1-8 alkylsulfonylmethyl, cyano, nitro; or -C(O)-Y 4 , wherein Y 4 is hydrogen, C 1-8 alkyl, C 1-8 alkoxy, hydroxy or phenyl; R 2 is hydrogen, C 1-8 alkyl, C 1-8 haloalkyl, C 1-8 alkoxyalkyl, aryl, or arylC 1-8 alkyl; R 4 is as defined for Y 1 except for hydrogen; X and Y each is independently hydrogen, hydroxy, halogen, cyano, C 1-8 alkyl, C 1-8 alkoxy, C 1-8 alkoxycarbonyl, C 1-8 alkoxycarbonyloxy, hydroxyC 1-8 alkyl, C 1-8 haloalkyl, C 2-8 acyl, C 2-8 acyloxy, carbamoyl, carbamoyloxy, C 1-8 alkylthio, C 1-8 alkylsulfinyl, C 1-8 alkylsulfonyl or C 1-8 alkylsulfonyloxy; aryl, aryloxy, arylS(O) p , arylsulphonyloxy, each of which may in turn be substituted by 1 to 3 substituents selected from halogen, C 1-8 alkyl, C 1-8 haloalkyl, C 1-8 alkoxy, C 1-8 haloalkoxy, nitro, cyano, C 1-8 alkylthio, C 2-8 acyl; amino or together represent =O, =S, =NH, =NOR 12 or =CR 13 R 14 ; or X and R together may form a bridge having the formula -C(O)-O-, -C(O)-S or -C(O)-NR 2 - wherein the carbonyl is attached to A; p is 0, 1 or 2; X 1 , X 2 and X 3 are independently hydrogen, hydroxy, C 1-8 alkoxy, C 1-8 alkylthio, hydroxyC 1-8 alkyl or hydroxybenzyl whereby at least one of X 1 , X 2 and X 3 is other than hydrogen; or X 3 is hydrogen and X 1 and X 2 together form a 4- or 5-membered bridge comprising elements selected from -O(CH 2 ) n' -O-, -OC(O)(CH 2 ) m O- and -S(CH 2 ) n' S-; R 7 and R 8 are each independently (a) hydrogen, halogen; (b) C 1-24 alkyl, C 2-8 alkenyl, C 2-8 alkynyl, C 1-8 alkoxy, C 1-8 alkoxyC 1-8 alkoxy, C 2-8 alkenyloxy, C 2-8 alkynyloxy, C 1-8 alkylthio, C 2-8 alkenylthio or C 2-8 alkynylthio, each of which may in turn be substituted by 1 to 6 halogen atoms; (c) C 3-6 cycloalkyl, C 3-6 cycloalkylC 1-8 alkyl, heterocyclyl, heterocycloC 1-8 alkyl, heterocycloC 1-8 alkoxy, aryloxy, arylC 1-8 alkoxy, or arylC 1-8 alkylthio, each of which is unsubstituted or may be substituted by 1 to 3 substituents selected from (i) halogen; (ii) C 1-8 alkyl, C 1-8 alkoxy, C 1-8 haloalkoxy, C 1-8 haloalkyl, C 1-8 alkylthio, C 1-8 alkylsulfonyl, C 1-8 alkylsulfonylmethyl; and (iii) nitro, cyano, acyl, amino; (d) amino, amido, aminosulfonyl, cyano, nitro, or -(CHR 4 ') n '''-C(O)Y 4 ', wherein Y 4 ' is hydrogen, C 1-8 alkyl, C 1-8 alkoxy or hydroxy and n''' is 0, 1, 2 or 3; R 4 ' is as defined for Y 1 ; R 12 is hydrogen or C 1-8 alkyl; R 13 and R 14 are independently hydrogen, C 1-8 alkyl or halogen; m is 1 or 2; n is 0, 1 or 2; and n' is 2 or 3; with the proviso that when R is carboxyl in free ester or salt form and X and Y together are =O one of rings A and B contains a hetero atom. A compound of formula (I) according to Claim 1 wherein A is pyridyl, quinolyl, pyridyl-N-oxide, pyrimidinyl, pyrazinyl, thienyl or furyl. A compound of formula I according to claim 1 wherein the ring system A is selected from phenyl, pyridyl or pyridyl-N-oxide, R is a carboxyl group which may be in the form of the free acid or in ester or salt form, a thiocarboxyl group which may be in the form of the free acid or in ester form, a carbamoyl group, or a group -CONR 7 R 8 , Y 1 , Y 2 and Y are attached to carbon atoms and are independently hydrogen, halogen, C 1-8 alkyl, C 1-8 alkoxy; each of W 1 , W 2 , W 3 and W 4 is independently CH, CR 3 or nitrogen; R 1 and R 3 each is independently hydrogen, halogen, C 1-8 alkyl, C 1-8 alkoxy, aryloxy or arylC 1-8 alkoxy, X and Y each is independently hydrogen, hydroxy, cyano, C 1-8 alkoxy, C 2-8 acyloxy or together represent =O; or X and R together form a bridge having the formula -C(O)-O- or -C(O)NR 2 - whrein the carbonyl is attached to A. A compound of formula I according to claim 1 wherein ring system A represents phenyl, pyridyl or thienyl; B represents pyrimidinyl or triazinyl; R represents a ring C especially oxazole, oxazolone, oxazolidine or oxazolidinone; carboxyl in the form of the free acid or in ester or salt form; -CONR 7 R 8 , cyano or together with X represent -C(O)-O- or -C(O)NH 2 -, Y 1 , Y 2 and Y 3 each represent independently hydrogen, halogen, C 1-8 alkyl, C 1-8 alkoxy, C 1-8 alkylthio or arylthio, X, Y each represent independently halogen, hydroxy, C 1-8 alkoxy, C 1-8 acyloxy, a ring B, halogen, C 1-8 alkylthio or arylthio or together =O or =NH, and and R 1 and R 3 each represent independently halogen, C 1-8 alkoxy, C 1-8 alkyl, C 1-8 halogalkoxy, aryloxy, arylC 1-8 alkoxy, C 2-8 alkynyloxy, C 2-8 alkenyloxy. A compound according to claim 4, wherein Y 1 , Y 2 and Y 3 additionally may each represent independently arylC 1-8 alkoxy, C 2-8 alkenyloxy, or C 2-8 alkynyloxy, B is especially pyrimidinyl, particularly 4,6-dimethoxy-2-pyrimidyl, A is especially phenyl or pyridyl substituted as defined above, X and Y are preferably hydrogen, halogen, cyano, hydroxy, alkoxy or together =O, especially hydrogen, hydroxy or together =O. A compound according to claim 1 wherein X and Y are together =O. The compound sodium 3,6-dichloro-2-[(4,6-dimethoxypyrimidin-2-yl) carbonyl]benzoate according to claim 1. A herbicidal composition comprising an herbicidally effective amount of a compound of formula (I) according to Claims 1-7. A method for combatting weeds which comprises applying thereto or to a locus thereof an herbicidally effective amount of a compound of formula (I) according to Claims 1-7. A process for preparing a compound of formula (I) according to Claim 1 comprising a) when X and R combine to form a bridging group as defined in claim 1 and Y is hydrogen, cyano, arylthio, arylsulfinyl or arylsulfonyl, reacting a compound of formula II wherein ring A, Y 1 , Y 2 and Y 3 are as defined in claim 1, Y' represents hydrogen, cyano, arylthio, arylsulfinyl or arylsulfonyl and Z 1 represents oxygen, sulfur or NR 2 wherein R 2 is as defined in claim 1 with a compound of formula III wherein W 1 , W 2 , W 3 , W 4 and R 1 are as defined in claim 1 and R 21 represents methylsulfonyl or halogen to obtain the corresponding compound of formula Ip b) treating a compound of formula Ip wherein Y' represents cyano or arylsulfonyl and Z 1 represents oxygen and the other symbols are as defined in claim 1; (i) by hydrolysis to give a corresponding compound of formula I wherein R and X form a bridge and Y is hydroxy or a compound of formula I wherein X and Y together form =O; (ii) with an amino to give a corresponding compound of formula I wherein R is an optionally substituted carbamoyl group and X and Y together form =O; (iii) with a group MOR 22 wherein M is an alkali metal and R 22 is hydrogen or C 1-8 alkyl, to give a corresponding compound wherein R and X form a bridge and Y is hydroxy or C 1-8 alkoxy; c) hydrolyzing a compound of formula Ip wherein Y' represents hydrogen, Z 1 represents oxygen and the other symbols are as defined in claim 1 to give a compound of formula I wherein R is a carboxyl group optionally in salt form, X is hydrogen and Y is hydroxy; d) ring opening a compound of formula Ip wherein Y' represents hydroxy, Z 1 represents oxygen and the other symbols are as defined in claim 1 to give a compound of formula I wherein R is a carboxyl group optionally in salt form and X and Y together are =O; e) esterifying a compound of formula I wherein R is a carboxyl group optionally in salt form and X and Y are =O and the other symbols are as defined in claim 1 to give the corresponding compound wherein R is a carboxyl group in ester form; f) halogenating a compound of formula Ip wherein Y' represents hydroxy, Z 1 is as defined in part a) and the other symbols are as defined in claim 1 to give a compound of formula I wherein X and R together form a bridging group and Y' is halogen; g) reacting a compound of formula Ip wherein Z 1 is oxygen, Y' is halogen and the other symbols are as defined in claim 1 with a group R 2 NH 2 and a group HOR 23 wherein R 23 represents C 1-8 alkyl, C 2-8 acyl or aryl and R 2 is as defined in claim 1 to give the corresponding compound wherein Z 1 is NR 2 and Y' is C 1-8 alkoxy, aryloxy or C 2-8 acyloxy; h) oxidizing a compound of formula Ip wherein Y' represents hydrogen, Z 1 is as defined in part a) and the other symbols are as defined in claim 1 to give the corresponding compound wherein Y' represents hydroxy; i) reacting a compound of formula IV with a compound of formula V to produce a compound of formula Iq wherein ring A, R, R 1 , W 1 , W 2 , W 3 , W 4 , Y 1 , Y 2 and Y 3 are as defined in claim 1 and X'' and Y'' are hydrogen and R 24 is C 1-8 alkyl, j) mono- or di-halogenating a compound of formula Iq wherein X'' and Y'' are hydrogen and the other symbols are as defined in part i) to produce the corresponding compound of formula Iq wherein one or both of X'' and Y'' are halogen; k) oxidizing a compound of formula Iq wherein X'' and Y'' are both hydrogen or X'' is halogen and Y'' is hydrogen and the other symbols are as defined in claim 1 to produce the corresponding compound wherein X'' and Y'' together represent =O or one represents hydrogen and the other represents hydroxy; l) alkylating a compound of formula Iq wherein X'' represents hydrogen and Y'' represents hydrogen and the other symbols are as defined in claim 1 to produce the corresponding compound wherein X'' represents C 1-8 alkyl and Y'', represents hydrogen; m) introducing a C 1-8 alkoxy or C 1-8 alkylthio group into a compound of formula Iq wherein X'' represents halogen, Y'' represents hydrogen and the other symbols are as defined in claim 1 to produce the corresponding compound wherein X'' represents C 1-8 alkoxy or C 1-8 alkylthio and Y'' represents hydrogen; n) acylating a compound of formula Iq wherein X'' represents hydroxy, Y represents hydrogen and the other symbols are as defined in claim 1 to produce the corresponding compound wherein X'' represents acyloxy and Y'' represents hydrogen; o) reacting a compound of formula Ip wherein Z 1 is oxygen, Y' is hydrogen and the other symbols are as defined in claim 1 with a group R 7 NH 2 wherein R 7 is (a) hydrogen, halogen; (b) C 1-24 alkyl, C 2-8 alkenyl, C 2-8 alkynyl, C 1-8 alkoxy, C 1-8 alkoxyC 1-8 alkoxy, C 2-8 alkenyloxy, C 2-8 alkynyloxy, C 1-8 alkylthio, C 2-8 alkenylthio or C 2-8 alkynylthio, each of which may in turn be substituted by 1 to 6 halogen atoms; (c) C 3-6 cycloalkyl, C 3-6 cycloalkylC 1-8 alkyl, heterocyclyl, heterocycloC 1-8 alkyl, heterocycloC 1-8 alkoxy, aryloxy, arylC 1-8 alkoxy, or arylC 1-8 alkylthio, each of which is unsubstituted or may be substituted by 1 to 3 substituents selected from (i) halogen; (ii) C 1-8 alkyl, C 1-8 alkoxy, C 1-8 haloalkoxy, C 1-8 haloalkyl, C 1-8 alkylthio, C 1-8 alkylsulfonyl, C 1-8 alkylsulfonylmethyl; and (iii) nitro, cyano, acyl, amino; (d) amino, amido, aminosulfonyl, cyano, nitro, or -(CHR 4 ') n '''-C(O)Y 4 ', wherein Y 4 ' is hydrogen, C 1-8 alkyl, C 1-8 alkoxy or hydroxy and n''' is 0, 1, 2 or 3, R 4 ' is as defined for Y 1 ; to give a compound of formula I wherein R is monosubstituted carbamoyl, X is hydrogen and Y is hydroxy; p) sulfonylating, carbamoylating, acylating or carbalkoxylating a compound of formula Ip wherein Z 1 is oxygen, Y' is hydroxy and the other symbols are as defined in claim 1 to produce the corresponding compound of formula I wherein R and X form a -C(O)-O- bridge and Y represents sulfonyloxy, carbamoyloxy, C 2-8 acyloxy or C 1-8 alkoxycarbonyloxy; q) reacting a compound of formula Ip wherein Z 1 is oxygen, Y' is halogen and the other symbols are as defined in claim 1 with a group R 7 R 8 NH wherein R 7 is as defined in part o) and R 8 is as defined for R 7 to give a compound of formula I wherein R is disubstituted carbamoyl, and X and Z together represent =O; and recovering any compound wherein R is a carboxyl or thiocarboxyl group in free form or in ester form and any compound wherein R is carboxyl in free form or in salt form.

Inventors: ANDERSON RICHARD JAMES, CLOUDSDALE IAN STUART, HOKAMA TAKEO, ANDERSON, RICHARD JAMES, CLOUDSDALE, IAN STUART, HOKAMA, TAKEO
Applicants: CIBA GEIGY AG, SANDOZ AG, NOVARTIS AG, SANDOZ-ERFINDUNGEN VERWALTUNGSGESELLSCHAFT M.B.H., SANDOZ-PATENT-GMBH
Application year: 1991
Main classification: C07D405
IPC codes: C07D251, C07D405, C07D417, C07D401, A01N43, C07D471, C07D213, C07D413, C07D491, C07D403, C07D239, C07D409