CA2132746A1 - Herbicides - Google Patents

Abstract

A herbicidal composition comprises ester, amide, aryl and heterocyclic derivatives of monic acid A, monic acid B, monic acid C, monic acid ketone and pseudomonic acid. Novel monic acid esters may be represented by the formula (mon)-CO-XR3 wherein (mon) is a residue of a monic acid compound, (mon)-COOH, X is O or S and R3 is an alkyl group substituted by a group -A-R11 wherein A is O or a group S(O)x, and R11 is an optionally substituted alkyl, alkenyl, alkynyl, phenyl, alkyl carbonyl, cycloalkyl or heterocyclyl group.

Description

W O 93/19599 P~/GB93/00542 HE~BICIDES

This invention relates to chemical compounds useful as herbicides, to processes for preparing them and to herbicidal composi~ions and processes utilising them.
A number of derivatives of monic acid are known to have utility as biologically active compounds for use in human and veterinary medicine.
Such compounds are described inter alia in GB 1587058.
Ue have now found that certain monic acid derivatives, including es~ers, amides and salts have a novel and unexpected herbicidal activity.
According to the present invention there is provided a herbicidal co~position comprising a compound of the formula ~I3 or (IA) or ~IB) in admixeure with a herbicidally acceptable carrier or diluent, wherein Y
represents (IC) or (ID) or (~E~ and wherein R2 is a group Co-xR3 wherein X
is 0 or S and R3 is hydro~en or an agrochemically acceptable ester-forming radical; or R2 is a group -R4 wherein R4 is an optionally substituted aryl or heterocyclic group; or R2 is a group Co-NR5R6 wherein R5 and R6 are the same or different and each represent an agrochemically acceptable amide-forming radical; stereoisomers of the compounds of formula (I), (IA) and (IB) and salts of the compound of formula (I), (IA) and (IB) wherein R2 ::
is ~oXR3, X is 0 and R3 is hydrogen.
According to a further aspect of the present invention there is pro~ided a process of severely damagi~g or killing un~anted pla~ts, which - comprises applying to the plants, or to the growth medium of the plants, a herbicidally effec~ive amount of a compound of ~he formula (I) or (IA) wherein Y represents ~IC) or (ID) or (IE~;
R2 is a group Co-XR3 wherein X is 0 or S and R3 i~ hydrogen or an agrochemically accep~a~le es~er-forming radical; or R2 is a group R4 wherein R4 is an optionally substituted he~erocyclic group; or R i5 a group -C~-N~-CH2-CO-~ ~herein U is hydr~gen, optionally subs~itu~ed phenyl, optionally substituted C1 to C2~ alkyl, optionally substitu~ed C2 to CB alkenyl, optionally substitueed C2 ~o C8 al~ynyl, optionally substituted heterocy~lyl or C3 to C7 cycloalkyl; or R i5 a grsup -C0-NH-NH2 or -C0-N~-N~-C0-Y wherein Y is op~ionally substituted C1 to C20 alkyl, optionally substitueed C2 to CB alkenyl, optionally substltuted aryl, optionally substituted aralkyl or optionally substituted heterocyclyl; or R2 is a group co-NR5 R6 wherein R5 and R6 are the same or differen~ and s~T~ B 9 ~ I O ~ 5 4.2 ,~ sY 1~4 each represent (a) hydrogen, or (b) C1 20 alkyl, C2 8 alkenyl, either o~
which may be optionally substituted with C3 7 cycloalkyl, halogen, carboxy, Cl ~ alkoxycarbonyl, carbamyl, aryl, heterocyclyl, hydroxy, C1 &
alkanoyloxy, amino, mono- or di-(C1 6)alkylamino; or (c) C3 7 cycloalkyl optionally substituted with Cl 6 alkyl; or (d) optionally substituted aryl; or (e~ optionally substituted heterocyclyl; or (f) R5 and R6 together with the nitrogen atom to which they are attached represent an optionally substituted C5 7 heterocyclic ring; or R2 is a group -C0-0-R wherein R is a C3 20 alkyl, C3 8 cycloalkyl, C4 20 alkenyl, aralkyl, cycloalkylalkyl, heterocyclyl or heterocyclylalkyl group which group is substituted with a ketonic oxo group; or R7 is a group -CH2-CoR13 wherein R13 is acyl, aralkyl, amino, ureido or carbamic acid ester residue, :
and stereoisomers of the compound of formula (I) and salts of the compound of formula (I) wherein X is 0 and R3 is hydrogen.
The term "aryl" as used herein includes phenyl, and naphthyl optionally substituted with up to five substituents which may be independently selected from halogen, C1 6alkyl, C1 6alkoxy, Cl 6alkylthio, balo(Cl 6~alkyl, hydroxy(C1 ~)alkyl, halo(C1 6)alkoxy, C2 8 alkenyl, C2 8 alkeneoxy, C2 8 alkenylthio, ~ ~ alkynyl, C2 8 alkyneoxy, C2 8 alkynylthio, hydroxy, cyano, nitro, amino, mono- and di- C1 6 alkylamino, Cl 6 alkanesulphinyl, C1 6 alkane sulphonyl, carboxy, C1 6alkoxycarbonyl, and Cl ~alkoxycarbonyl(C1 6~alkyl groups.
The term "aralkyl" as used herein includes groups in which the aryl ~oiety is a phenyl group which may be optinnally substituted as hereinbefore defined for aryl and in whish the alkylene radical has from 1 to 4 carbon atoms.
The term "heterocyclyl" as used herein includes aliphatic or aromatic single or fused rings comprising up to four hetero atoms in the ring selected from oxygen, nitrogen and sulphur and optionally substituted with aryl, with another heterocyclic ring or with one or ~ore o~ those substituents mentioned above as optional substituents for aryl.
When R2 is a group Co-XR3, X is preferably 0.
Suitable ester-forming radicals, R3, include optionally subst;tuted C

. " .,, " .. .. . .. . ... . .. .
C~ -'.sv3 ~ F~ ET~ T

9 3 1 0 0 5'~
t) ~ 3 a~ MAY 1994 - 2a -to C20 alkyl, optionally substituted C2 to C20, for example C2 to C~
alkenyl, optionally substituted C2 to C20, for example C2 to C8 alkynyl, .'.

_ ;V3 ~ $~

' 7 ~ JQ~4 optionally substituted C3 to C7 cycloalkyl, optionally substituted aryl or optionally substituted heterocyclyl.
Optional substituents which may be present in optionally substituted alkyl, alkenyl or alkynyl groups, such as those represented by R3, include C3_7 cycloalkyl, C1_l0 alkoxy, C1 l0 alkylthio, C2 8 alkenoxy, C2 8 alkenylthio, C2 8 alkyneoxy, C2 8 alkynylthio, halogen, halo-C1 10 alkoxy, halo-C2 8alkeneoxy, halo-C2 8alkynoxy, carboxyl Cl 6alkoxycarbonyl, carbamoylt optionally substituted aryl, optionally substituted heterocyclyl, hydroxy, cyano, nitro, Cl 6alkanoyloxy, a~ino, mono- and di-(Cl 6)alkylamino.
Optional substituents w~ich may be present in C3 7cyclo~1kyl groups, :::
such as those represented by R I include Cl 6alkyl halo-Cl 6alkyl, C1 10 alkoxy, C1 10 alkylthio, C2 8 alkenyl, C2 8 alkeneoxy, C2 B alkenylthio C2 8 alkynyl, C2 8 alkyneoxy, C2 8 alkynylthio, halogen, carboxy, Cl 6 alkoxycarbonyl, carbamoyl, optionally substituted aryll optionally substituted-heterocyclyll hydroxy, cyanol nitro, C1_6alkanoyloxyl amino, ~:
mono- and di-(Cl 6)alkylamino.
When R3 is alkyl, optionally substituted by aryl it may be regarded as ~-an aralkyl group as defined above.
Suit~ble ester-forming radicals R3 also include Cl to C10 alkyl optionally substituted by hydroxy, halogen, cyano. Suitable ester-forming radicals R3 also include C2 to C10, for example C2 to C4 alkenyl, for example vinyl, prop-2-ene-1-yl, and but-1-ene-4-yl which may be unsubstituted or op~ionally substituted by hydroxy by halogen or by cyano prsvided that the alkenyl group is not substituted by hydroxy when it is a vinyl groupO
A further preferred group R3 is a C1 1~ alkyl group, and preferably a C1 4 alkyl ~roup, substituted by a group -A-R wherein A is O or a group S()x wherein x is O, 1 or 2 and R11 is an optionally substituted Cl to C10, and preferably optionally substituted Cl_6, for example C1 to C4 alkyl group, an optionally substituted C2 to C8, and preferably optionally substitued C2 6~ for example C2 to C4 alkenyl group, an optionally substitued C2 to C8, and preferably optionally substitued C2 6~ for example C2 to C4 alkynyl group or an optionally substituted phenyl group, an S~ E~
' J' ;:._atloil I
-J ~ 0 5 ~`2 04 MAY t994 7 ~ ';3 - 3a - -optionally substituted Cl 6 alkyl carbonyl group or an optionally substituted C3 7 cycloalkyl group, for example an optivnally substituted C3 6 cycJoalkyl group, or an optionally substitututed C3 7 heterocyclic group, for example an optionally substituted aliphatic heterocyclic group, for example an optionally substituted oxygen-sontaining al;phatic ~
heterocyclic group. An example of a group R3 having thi~ substitution is `
the group -~CH2)n,-A-CH-CH-R12 wherein n' is an integer from 1 to 4 and R12 is hydrogen or a C1 $o C4 alkyl group. A is preferably oxygen.
Optional substituents may be thosë indicated above for alkyl, alkenyl, alkynyl and aryl respectively.

,. "; , . . - `,, C,',',;~2~ S~T
P~,T 1~ J. J;3cation W O 93/lg~99 ~ ~ 3 2 ~ PCT/GB93/00542 Unless otherwise specified, alkyl, alkenyl and alkynyl groups, including for example those present in R3, may be straight or branched chain groups.
Salts of the compound of formula (I) (IA) and (IB) wherein R2 is the group co-xR3 and in which X is 0 and R3 is hydrogen include for example metal salts, e.g. aluminium, alkali metal salts, such as sodium or potassiu~ alkaline earth metal salts, such as calcium or magnesium, and ammonium or substituted ammonium salts for example those with lower alkyl-amino such as triethylamine, hydroxy-lower alkylamines such as 2-hydroxyethylamine, bis(2-hydroxyethyl)-amine, or eri-(2-hydroxyethyl)-amine, cycloalkylamincs such as bicyclohexyl-amine, or with pro~aine, dibenzylamine, N,N-dibenzyl-ethylenediamine, Nethylpiperidine, N-benzyl-~-phenethyl-amine, dehydroabietylamine, N,N'-bis-dehydroabietylethylenediamine, or bases of th~ pyridine type ~such as pyridine, collidine, or quinoline) or trimethylsulphonium.
Uhen R2 is an optionally substituted heterocyclic group -R4, preferred heterocyclic gruups R4 include groups of formula (II) wherein R14 and R15, which may be the same or different, are independently selected from hydr~gen, optionally substituted phenyl, optionally substituted C1 to C20 al~yl, optionally substi~uted C2 to C8 alkenyl, optionally substituted C2 t~ C8 alkynyl, optionally substituted heterocyclyl or C3 to C7 cycloalkyl or from those general substituents for heterocyclyl listed above, X is a divalent group, -Y'-C~C- and Y' is oxygen or sulphur.
Preferably R4 is an optionally substitu~ed heterocyclic ring of formula (III) ~herein Y is 0 or S and R14 and R15 have the meanings given previously. An especially preferred group R4 is an optionally subs~itueed oxazol-Z-yl group, for example a group of formula (IV) ~herein R14 has the meaning given previously.
Alternatively R4 may be a group of formula (IY) uherein R14 is itself an optionally substituted heterocyrlic group, for example a group of the formula (IVa), (IVb) or ~I~c) in which formulae R16, R17, and R18 may be the same ~r different each is selected from hydrogen, halogen9 opeionally substitueed (Cl 6~alkyl, aryl, aralkyl9 heterocyclyl, (Cl 6)alkoxy, hydroxy, carboxy and salts thereof, (Cl 6)alkoxycarbonyl, carbamoyl, mono-or di-(Cl 6)~1kylcarb~moyl, sulphamoyl, mono- and di-(C1_6)alkylsulphamoyl, cyano~ nitro, amino, mono-and di-(Cl 6)alkylamino, acylamino, ureido, ~Cl 6)-alkoxycarbonylamino, (Cl 6)alkoxyimino, 2~2,2-trichloroethoxy~arbonylamino, acyl, (Cl 6)alkylthio, arylthio, wo 93/lg599 ~ t ~ 2 7 t ~ PCT/GB93/00542 (C1 6~alkanesulphinyl, arysulphinyl, (Cl 6)alkanesulphonyl and arylsulphonyl. .
Suitably, R14 is a group of formula (IVc) and R16, R17 and R18 are preferably hydrogen.
A further suitable ester-forming radical R3 is a group R7 wherein R7 represents an optionally substituted C3 20 alkyl, for example C3 10 alkyl, C3 8 cycloalkyl, C4 20 alkenyl, aralkyl, cycloalkylalkyl, he~erocyclyl or heterocyclylalkyl group which group is additionally substitu~ed with a ketonic oxo group.
Thus one sub class of the group R2 when it is a group -Co-oR7 is a group of formula (V) wherein Z is an optionally substituted C to C12 a}kylene group (-(C~2)n~ ~ wherein n'' is from 1 to 12) and R~ represents a Cl 10 alkyl, C3_8 ~ycloalkyl, C2 10 alkenyl, C2_10 alkynyl, aryl, aralkyl, cycloalkylalkyl or heterocyclyl group, each of which may be optionally substituted. Optional substituents may be those specified above for the groups alkyl, cycloalkyl, alkenyl, aryl and heterocyclyl respectively.
A further sub-class of the group R2 is a group Co-~R7 and R7 is a ::~
group -C~2-Co-R13 wherein R13 is suitably a carbamic aeid ester residue.
By the term "carbamic acid:ester residue" is meant a group of general formula -N(Rl9)-CO-NR20R21 wherein Rl9 is hydrogen or an optionally ~subs~t~itued Cl ~ alkyl group and R20 and R21 are ~ndependently selected from hydrogen or any of the groups R5 and R6 give~ below.
As exampIes of suita~le agrochemically acceptable amide-forming radicals R5 and R6, whi:ch:-may be the same or different, there may be mentioned:
: (a) hydrogen or:
: :(b) ah optionally;substituted Cl 20 alkyl group, an optionally substituted C2 20, for example C2 8 alkenyl group or an optionally substituted C2 20? for example C2 8 alkynyl group or (c) optionally substituted C3 to C7 cycloalkyl or (d) optionally subs~ituted aryl or ~e) opt~onally substituted heterocyclyl; or (f~ R5 ant R6 together with the nitrogen atom to which they are attached represent an optionally substituted C5 7 heterocyclic ri~g or d d R6 is a group -NR22-N23R2 wherein R is hydrogen or C1 6 alkyl are R23 and R24, which may be the same or different, may independently take any of the meanings given for :

3 6 - PCT/GB93/flO542 R5 and R6 under (a)t (b), (c), (d), (e) and (f) above or (h) R6 is a group -NR22_N=CR23R24 wherein R22, R23 and R have the meanings given previousIy or (i~ R is hydrogen and R6 is a group -CR25R26-Co-U or - NR27-Co-U
wherein W is optionally substitu~ed phenyl or optionally substituted heterocyclyl, R25, R26 and R27 are indendently hydrogen or optionally substitued C1 6 alkyl groups.
Preferred agrochemically acceptable amide-forming groups R5 and R6 are those wherein R5 is hydrogen or a Cl 4 alkyl group and R6 is a Cl_4 alkyl group, each of which alkyl groups may independently be optionally substitute~ by C3 7 cycloalkyl, C1 4 alkoxy, halogen, carboxy, C1 6 alkoxycarbonyl, carba~yl, optionally substituted aryl, optionally sub~tieuted heterscyclyl, hydroxy, C~ 6 alkanoyloxy, a~ino, mono- or di-(Cl ~)alkylamino or wherein R5 and R6 together uith the nitrogen atom eo which they are attached represent an optionally substituted C5 6 aliphatic heterocyclic ring. As examples of suitable groups wherein R5 and R6 toge~her with-the nitrogen a~om to which they are attached form an optionally substituted C5 6 het~rocyclic ring~ there may be mentioned morpholinyl, piperidyl, piperazinyl, or pyrollidinyl, each of which may be optio~ally substitu~ed by halogen or Cl 4 alkyl~
~ hen R5 is hyd~ogen and R6 is a group -CR25R26-Co-U or - NR27-CO-U, R25, R26 and R27 are pref~rably hydrogen and U is preferably optionally substituted phenyl or an~optionally substituted 5 or 6~membered heterocyclic ri~g co~aini~g from 1 to 3 heteroatoms selected from oxygen, ni:trogen and sulphur, for i~stance thienyl or furanyl.
Suitable substituents for ~ ~hen it is a phenyl or heterocyclyl group include those men~ioned previously and especially halogen, Cl to C6 alkyl, C~ to C6 alkoxy, hydroxy~ carboxy, Cl-C6 alkoxycarbonyl, carbamoyl, mo~o-or di- (Cl to C~) albl car~amoyl, sulphamoyl, mono- and di-~Cl to C6) sulphamoyl, cyano, for example m- or p- cyano, nitro, amino, mono- and di-(C1 to C6) alkylaminot C1 to C6 acylamino9 ureido, Cl to C6 alkoxycarbonylamino, Z,2,2-trichloroethoxycarbonylamino, Cl to C6 alkan~yl, C1 to C6 al~ylthiot Cl to C6 alkanesulphinyl, and Cl to C6 alkanesulphonyl Certain compounds of for~ula (I), (IA~ or (IB) are novel.
According to a further aspect of the present invention there is provided a compound of t~e formula (I) or (IA) or (IB3 above wherein R2 is a group Co-xR3 x, is 9 or 5 and R3 is a C~ 10 alkyl group substituted by a group ~A-R11 wherein A is O or a group S()X wherein x is 0, 1 or 2 and R

W O 93/1959g P&T/GB93/00~42 ~ 7 .7~t 3 ?.7`i~ f!
is an op~ionally substituted ~1 to C10 ak~-l group, an optionally sub~tituted -2 to C8 alkenyl group, an c icnally substitued C2 to C8 ~ vnyl gro-~p, an optio~ally substitute ^~nyl group, an optionally s~Dstituted C1 6 alkyl carbonyl group, optionally substituted C 7 cycloalkyl group or an optionally substituted C~ 7 heterocycli. group provided that R3 is not a ~roup -(CH2)2- when R is ethyl-Optional substituents may be those indicated previously as suitable for alkyl, alk~nyl, alkynyl, phenyl, cycloalkyl or heterocyclyl ~::
retrospective~y. `~
Preferably, R3 is 2 1 4 alkyl group substituted by a group -A-R
wherein A is O or a group S()x wherein x is 0, 1 or 2 and R is an optionally substituted Cl to C6 akyl group, an optionally substituted C2 to ~:
: C6 alkenyl group, an optionally substitued C2 to C6 alkynyl group, an optionally substituted phenyl group, or a~ optionally substi~u~ed Cl-6 alkyl carbonyl group, an optlonally substitued C3 6 cycloalkyl group or an optionally subs~ituted aliphatic C3 7 oxygen-conta~ning heterocyclic group, provided that R is not a group -(C~2)2- when Rl1 is ethyl.
In one embodiment of the present invention9 R3 is the group -(G~2)n,-A~CHSCB-Rl2 wherein n' is an integer from 1 to 4 A is O or a group S(~x ~herein x is 0, 1 or 2 and R is hytrogen or a Cl to C4 alkyl gro~p.
Compounds of formula (I) uherein R' is the group COO~ and wherein Y
:represents {IC~ or (ID) or ~IE) are disclosed in Uest German O~fenlegungsschriften~No. 2726619, 2726618 and 2848687 and European Pazent Application No 79300371.6. Such compounds having the tri-substitu~ed double bond in the E-configuration are referred to as monic acid C, monic ::
a~id A and monic acid B respecti~ely. Pre$erably the compounds of the prese~t invention are deri~atiYes of Monic acid A. ~owever, the compounds o~ the present invention may exist in the ~ (natural~ and Z (or iso) :
geometrical forms in respect of the tri-substituted double bond. The stereochemistry of ~he compound of formula (I) is thus preferably defined such that the moiety (VI) is that moiety having the trivial name "normonyl"
(3-l~2S,3R,4R,5S)-5-{(2S,3: ~S,5S)-2,3-epox~-~-hydro~y-4-methylhexyl}--3,4-dihydroxytetrahydropyran-2-yll-2-methyl-l(E)-enyl radical) such that when R2 is the group -COO~, the compound of for~ula (I) is monir acid A.
Compounds of formula ~I) may ~hus conveniently be named as (1-normonyl) derivatives and esters of monic acid A are conveniently na~ed as monate A
esters. It uill be appreciated that in compounds of formula (I), the group W 0 93/l9599 ~ PCT/GB93/00542 R may conta}n one or more chiral centres. The present invention enrompasses all such resultant isomeric possibilities.
Particular examRles of compounds for use in the composition of the invention are illustrated in Table 1 below wherein the compound is of formula (I) and the stereochemistry of the moiety (VI) is that of the "normonyl" radical as described ab~ve. Table 2 lists examples of compounds for use in the composition of the present invention wherein the compound is of formula (IB), being derivatives of pseudomonic acid. Table 3 lists examples of compound for use in the composition of the present invention wherein the compound is of formula (I) and Y is of formula (IC), being derivatives of monic acid C.
I~ will be readily appreciated that compounds having values of R2 corresp~nding to those listed in Table 1 may be prepared wherein the compound is of for~ula (I) and Y is of the formula (IC) (being derivatives of monic acid C) and ~herein the compound is of formula ~IB) (being derivaeives on pseudomQnic acid) and such compounds should be considered as being specifically disc10sed herein. Corresponding derivatiYes of the compounds of formula (IA) and of formula (I) wherein Y is of formula (ID) and (IE~ may also b~ readily prepared and should similarly be considered as being~specifically disclosed herein.

- ~ 2 CO~POUND R
~U~BER
:
: 1 -COO~
2 C0 0 CH2 C~ C~2 3 -C0-0-CH2-C~2-OB

4 -C0-S-C~3 -C0-0-C~2c~2-~-c~H2 6 C0 ( 2)3 3 7 -co-o-~cH2)3-co-phenyl 8 -CO-O-C~2-CO-N~-CO-NH2 -CO-O-C~2CN
-C0-0-CH2-~3-cyanophenyl) 11 -C0-0-C~2-(3-bromophenyl) 12 -C0-0-CH2-(3-methylphenyl~

W O 93/19599 ~ ~3 ~ 7 ~-1 r~ PCT/GB93t~0542 _ 9 _ TABLE 1 (Continued) COMPOUND R
NUMBER

. _ . . . .
13 -CO-O CH2-(4-hydroxy~ethylphenyl) 14 -CO-NH-C~2-CO-(4-cyanophenyl) Structure YII
16 Structure VIII
17 -co-o-(cH2)8-Br 18 Structure IX
19 Structure X
-C0-0-(C~z)l5cH3 21 -CO-O-C~3 22 Structure XI
23 -CO-O-(C~2)2-~-C~2-C~C~2 24 _Co-o-cc~2)2-o-cH-~-c~3 _Co-o-(c~2)3-cH=c~2 26 _~o^o-(c~2)2-o-~2 ~ 3 27 -CO-O-(G~2)2-~-PhenYl 28 (CH2)2-O-(4-chlorophenyl) 29 -Co-o-(c3~)2 o_~o-c~3 (C~2)2-o-c~2-co-oc2Hs 31 -C--(C~2)3-C~C~
32 -Co-o-(c~2)4-o-c~c~2 33 -CO-O-(C~2)3-o-c~c~
34 -C~_o-(c~2)2-o-~E-cH-(c~2~3 C 3 -CO-O-C2~5 36 _CO-O-~B-~C~3)2 37 -CO-0~ 2)3-~3 3~ -CO-O-C~2-C(~3)3 39 -CO-O-(cyclohe~yl~
-CO-O-(cyclopropyl) 42 -CO-O-(C~2)2-0-(~H2)2-0-CH3 43 -C-~ 2)2- G~2 44 -CO-O-tC~2)2-0-CH2-~=C~Cl ~5 -co-o-~(c~3)-co-o-c2~5 W O 93/l9599 PCT/GB93/00542 TABLE 1 (Continued) NUMBER

46 -C--C~2-CQ-NH2 47 -CO-O-CHz-CH=C~Cl 48 -Co-o-c~ 3)-c~=c~2 49 CO O C~2 C~=C~C~3 -CO-O-phenyl 51 -CO-0-(4-chlorophenyl) 52 -CO-O-S3-nitrophenyl~
53 -CO-0-(4 methoxyphenyl~
54 -CO-0-(4-~methoxycarbonyl)-phenyl) -CO-O-C~2-~4-methoxyphenyl) 56 -CO-O-C~2-tfuran-2-yl) 57 -CO-O-CH2-CH2Cl - 58 -CO-NH-(2,:4-dichlorophenyl) : 59 -C0-NH-~2~5-dichlorophenyl) -CO-N(CB3)-(2,4-dichlorophenyl) 61 -CO-N~
62 -CO-NB-~2H5~
63 -CO-N~C2B5~2 ~: 64 -CO-morpholin-N-yl -CO-NB~2 6~ -CO-N~-CH2-CO-OC~H5 ~ 67 -Co-o-(c~2)2-s-c~3c~2 : 68 -CO-~-(C~2)2-0-C~sC~2 69 -C~-0-~2-0-C~--CO-O-C~2-(3-nitrophenyl) 71 -CO-O-C~2-C~C~
72 -Co-o-cH2-co-o-c2~5 73 -~0-0-(C~z)gC~
74 -CO-S-phenyl -~0-S-C~2-CO-0~3 76 -~0-0-CH2-0-C2~5 77 -CO-NH-(C~2)2-0~ ;

WO 93/19599 ~,~ A3 ~ 7 ~ ~ P~IGB93/00542 ;Y 1994 TA~I,E 1 (Continued) , COMPOUND R -NUMBER

.. . .
7~ -CO-N~- ( C~2 ) 2-0-C2~5 7 9 -CO-N( -C~2-C~=C~2 ) 2 Structure ~II
81 S~ructure ~III
82 -CO-NH-Nt CE~3 ) 2 83 -co-NEI-Nsc t C~3 ) 2 84 Structure XIV
St~ucture XV
86 -CO~ C~2-C~ .C~2 87 -CO-~(C~2-c~2-o~)2 8~ -C~-O (C~3)3S
93 -CO-O-CE~2-cyclopropyl 44 ~~ ~~ ( C~2 3 2-0-C~2-CE~ 2 C~2 3 -CO-O-(C~2)2-0-C H(C3~7)-CH=C~z 9~i, -CO-~ N~3-C~ 3 ) C~3 97 c~ o~ fN~ (c~ ~
99 -CO-O ~Na 100 -co~o~ 2-cH2 o-c~(c~3)-c~3 101 -CO-O-C~2-CZ~-O-C~3 10~ _~o-o-~H2-ca2-o-c~2-c~2 C~3 103 -CO-O-C~( C~3 ) -C~I2-0-C~I2-CE3 104 -~:o-O-~EI2-Ca2-0-~ ~y~l~pr~pYl ) 105 -C~C~2-ç~( ~H3 ~ -0-C~52-C~I3 106 -CO-~OC~3~ ;
... .

. . ?;~ q~T
== i W 0 93/lg599 P~T/GB93J00542 ~3~ 6 12 -(Pseudomonic acid deriatives) NUMBF.R

. . _ -CO-O-C~2-c~2-o-~=c~2 -CO-~-~2~5 91 -CO-O- ( CH2 ) 2-OH
92 -CO-N(C2H5)2 98 -CO-O N~-~C2~5)3 .

(monic acid ~ deriatives) ...._~
CO~POUND R
NUMBER

107 -CO-O~
108 -CO-O-C~2-C~2-O-c2H5 Compounds for use in ehe present invention are eieher kno~n compounds or may be prepared by methods analogous to those used for ~he preparation of corresp~nding known compounds.
The compounds may be regarded as derivat~ves of mo~ic acid which may be prepared by the selective hydrolysis of pseudomo~ic acid. ~ further useul starting material is the ketone ~hich may be obtained from pseudomonic acid by ozonolysis a~ -50 to -BOC as described for example in GB 1 587 060. Derivatives of pseudomonic acid may of course be prepared directly for pseudomonic acid as starting material.
In general it is desirable to protect the hydroxy groups during reactions of the the starting material surh as monic acid or derivatives thereof or the corresponding ketone. A wide variety of suitable pr~tectin~
groups is known and examples, are described for example in EP O 399 645.
Partîcularly suitable protecting groups are silyl groups since these are readily removed under mild conditions. Such groups are introduced by conventional silylating agents, including halosilanes and silaæanes. The - 13 ~
hydroxyl-protecting groups may subse~uently be removed by methods known in the art, including enzymatic ~ethods. For example silyl prote~ting groups may generally be removed by mild ~cid hydrolysis followed by alkaline hydrolysis as described for example by J P Clayton, K Luk and N H Rogers in Chemistry of Pseuodomonic acid, Part II J.C.S. Perkin Trans I, 1979, 308.
The compound No 1 of Table 1 is a known compound and may be prepared for example as described above. A more detailed preparation is given in Examples 2~ 3, 4 and 6 of GB 1,587,058. Salts of the compound of formula (I) wherein X is 0 and R3 is hydrogen (i.e. salts of Compound No 1 ~f Table 1) may also be prepared from monic acid by routine methods as described for example in GB 1,587,058. Typical processes include the reaction of monic acid ~ith a base, for example a hydroxide, carbonate or bicarbonate of the dQsired cation folloued by the removal of water; ion exchange with an appropriate resin; and reaction with amines.
Compound No 2 and Compound No 21 of Table 1 are know~ compounds and may be prepared for example as described in Examples 24 and 3 respectively of GB 1,587,059. General methods of preparing compounds of formula (I) wherein R2 is a group _coxR3 and X is 0 and R3 is an agrochemically acceptable ester-forming radical are also disclosed ln GB 1,587,059.
Compound No 3 of Table 1 is a known compound and may be prepared for ex~mple using the general methods described in GB 1,587,059 or as more specifically described in J Antibiot. 1988 41(5).
Compound No 4 of Table 1 is a known compound and may be prepared for example using the me~hods disclosed in EP 0 002 371 as more specifically disclosed in Example 5 thereof. Co~pounds uherein R2 in the compound of formula (I) is Co-xR3 and X is S may similarly be prepared using the general methods disclosed in EP 0 002 371.
Co~pound Nos 6 and 7 of Table 1 are known compounds and may be prepared for example as described in EP 0 025 288 and as more specifically described in Examples 2 and 5 thereof. Compounds ~herein R2 in the compound of formula (I) is a group of formula -Co-o-R7 and R7 is a C3 20 alkyl, C3 8 cycloalkyl, C4 20 alkenyl, aralkyl, cycloalkylalkyl~
heterocyclyl or heterocyclylalkyl group which group is substituted uith a ketonic oxo group, may be prepared using the general methods described in EP 0 025 288.
Compound No 8 of Table 1 is a kno~n compound and may be prepared for examp1e using the methods disclosed in Japanese patent No 54-151132.

W O 93/l9599 P~T/GB93/~542 C ~ o~ùnd No 10 of Table 1 is a known compound and may be prepared for example using the methods disclosed in EP 0 052 437, and as more specifically described in Example 2 thereof. Compounds of formula (I?
wherein R2 is a group -Co-oR3 may also be prepared as described in ~apanese Patent No 54-12376 or EP 0 052 437.
Compound No 14 of Table 1 is a known compound and may be prepared for example using the methods disclosed in EP 0 087 953, and as more spccifically described in Example 21 thereof. Compounds of formula (I) wherein R2 is a group -CO-NH-C~2-CO-U as hereinbefore defined may be prepared using the general me~hods set out in EP 0 087 953 where it is an intermediate in the manufacture of the compounds ~herein R2 is a heterocyclic group -R4 havi~g the formula (III) ab~ve which may similarly be prepared as described in EP 0 087 953. Thus for example, Compound No 19 may be prepared using an analogous method to that described in Example 14 of EP 0 087 953 (5-methyl~ normon-2-yl)oxazole or as more specifically described in J Chem Soc., Perkin Trans. I 1989 (11) 2059-63. Similarly, Compound No 22 of Table 1 may be prepared as described in Example 10 of EP 0 087 953.
Com~ound No 15~of Table 1 is a k~own compound and may be prepared for example using the methods disclosed in EP Q 123 378, and as more ~:
sp~ ically disclosed in Example 8 thereof. Cvmpounds of general formula wherein R2 is a group -CO-N~-N~2 or -C0-N~-N~-C0-U as hereinbefore defined may be prepared using the general methods described in EP 0 123 378 ~here such compound~ are in~ermediates to heterocyclic derivatives which ::
themselves provide further ex~mples of co~pounds of the general formula ~I) herein R2 is a group -R4.
Co~psund No 18 of Table 1 is a ~nown compound and may be prepared for ::
examp}e using the methods disclosed in EP 0 3g9 645, and as more specifically disclosed in Example 16 thereof. Compounds of general formula ~I) wherein R2 is a group -R4 having the for~ula (II) above may be prepared using the general methods of EP 0 399 645.
Compound of for~ula (I), (IA) or ~IB) wherein R2 is a group of formula CoNR5R~ may be prepared using the general methods described in EP 0 001 914.
In general therefore, typical processes for the manufacture of compounds of formula (I), (IA) or (IB) wherei~ R2 is the group -CooR3 include ~he reaction of a salt of monic acid (A, B or C~ or pseudomonic acid, for example an alkali metal salt, with a compound R3-L wherein L is a wo 93/19599 ~J ti '-? s.~ 7 ~ ~ P~r/GB93/005q2 leaving group such as halogen or mesolate to form an ester. The reaction suitably takes place in a solvent such as dimethylformamide or dimethylsulphoxide at a temperature in the range 10C to 100C and optionally in the presence of a co-solvent such as hexamethylenephosphonamide or N,N-dimethylpropyleneurea and optionally in the presence of a catalyst, such as an iodide catatlyst. If desired the salt of monic acid or pseudomonic acid may be prepared in situ, for example by treatment of the acid uith the appropriate base such as the carbonate.
Alternatively, compounds of formula (I), (IA) or (IB) wherein R2 is the group -CoxR3 or -CoNR5R6 may be prepared by the action of a compound R3X~ or R5R6N~ on a monic or pseudomonic acid or a simple activated :-~
derivative thereof. Suitably the raction takes place in a solvent such as :~:
tetrahydrofuran, diethyl ether, dichloromethane or chloroform and at a temperature in the range from -10C to 70C~
Other suitable methods of preparation of the compsunds for use in the compo~ition of the present invention are described in the literature with -:
specific reference to the patents and papers cited above.
The compounds~for use in the compositions of the present invention are ac~ive against a broad;range of weed species including monocotyledonous and dicotyledonous species. Many compounds sho~ good selectivity in crops, :~
pa~ticularly wheat, barley, maize, oil seed rape, su~ar beet and rice. The compoun~s for use in compositions of the present invention are preferably : applied directly to unwanted plants (post-emergence application) but they may also be applied:to the soil before the un~ansed plants emerge (pre-emergence application).
Thus acording to a:~further aspect of the present inYention there is provided a process of severely damaging or killing unwanted plants~ ~hich ~omprises applying to the plants or the the gro~th medium of the plan~s herbicidally effectiYe amount of a compound of the formula (I) or tTA) or (IB) as hereinbefor~ defined wherein R2 is as hereinbefore defined.
Novel compounds of the present invention are preferably used in the form of a composition co~prising a compound of for~ula (I) in admixture uith a carrier comprising a solid or liquid diluent.
Suitable compositions sf the present invention include both dilute compositions, which are ready for immediate use, and concen~rated compositions, which require to be diluted before use, usually with uater.
Preferably the compositions contain from 0.01~ to 90X by weigh~ of the active ingredient. Dilute compositions ready for use preferably contain W O 93/19~99 ~ PCT/GB93/00542 from 0.01 to 2% of active ingredient, uhile concentrated compositions may contain from 20 to 90X of active ingredient, al~hough from 20 to 70~ is usually preferred.
The solid compositions may be in the form of granules, or dusting powders wherein the active ingredient is mixed with a finely divided solid diluent, e.g. kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fuller's earth and gypsum. They may also be in the form of dispersible powders or grains, comprising a wetting agent to facilitate the dispersion of the powder or grains in liquid. Solid compositions in the form of a powder may be applied as foliar dusts.
Liquid compssitions may comprise a soIution or dispersion of an active ingredient in ~ater optionally containing a surface-active agent, or may comprise a solution or~dispersion of an active ingredient in a water-immisc~ble organic solvent which is dispersed as droplets in water.
Surface-active agen~s ~ay be of ~he cationic, anionic, or non-ionic type or mixtures thereof. The cationic agents are, for example, quaternary ammonium compounds (e.g. cetyltrimethylammonium bromide~. Suitable anionic agents are s~aps; salts of aliphatic mono ~ster of sulphuric acid, for example sodium lauryl sulphate; and salts of sulphonated aromatic -~
co~pounds, for example sodium dodecylbenzenesulphonate, sodium,calciu~, and a~onium lignosulphonate, butylnaphthalene sulphonate, and a mixture of the sodium salts of diisopropy~ and triisopropylnaphthalenesulphonic acid.
Suitable ~on-ionic agents are the condensation products of ethylene oxide with fa~ty alcohols such as oleyl alcohol and cetyl ~lcohol, or with alkylphenols such as~octyl- or nonyl- phenol (e.g. Agral 90) or octyl-cresol. Other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, for example sorbitan monolaurate; the condensation products of the par~ial ester with ethylene ox~de; the lecithi~s; and~silicone surface active agents ~wa~er soluble surface active agents ha~ing a skeleton ~hich comprises a siloxane chain e.g. Silwet L77). A suitable mixture in mineral oil is Atplus 411F.
The aqueous solutisns or dispersions may be prepared by dissolving the active ingredient in uater or an organic solvent optionally containing we~ting or dispexsing agent(s) and ehen, when organic solvents are used, adding the mixture so obtained to water optionally containing wetting or dispersing agent~). Suitable organic solvents include, for example, ethylene di- hloride, isopropyl alcohol, propylene glycol, diacetone 93~19599 - 17 ~ ) 3 ~ 7 ~ o PCT/GB93/00542 alcohol, toluene, kerosene, ~ethylnaphthalene, the xylenes and trichloroethylene.
The compositions for use in the form of aqueous solutions or dispersions are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, and the concentrate is then diluted with water before use. The concentrates are usually required to ~-withstand storage for prolonged periods and after such storage, to be capable of dilution with water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. Concentrates conveniently contain 20-90%, preferably 20-70X, by weight of the active ingredient(s). Dilute preparations ready for use may contain varying amounts of the active ingredient(s) dependi~g upon the intended purpose; amounts of 0.01~ to lO.OX and preferably O.lX to 2Z, by ueight of active ingredient(s) are normally used.
A preférred form of concentrated composition comprises the active ingredient wh$ch has been finely divided and which has been dispersed in ater in the presence of a surface-active agent and a suspending agent. -`
Suitabl~ suspending agents are hydrophilic colloids and include, for ;~
exa~ple, polyvinylpyrrolidone and sodium carboxymethylcellulose, and the vegetable gums, for example gum acacia and gum tragacanth. Preferred suspending agents are those which impart thixotropic properties to, and increase the viscosity of~the concentrate. Examples of preferred suspending agents include hydrated colloidal mineral silicates, such as montmorillonite, beidellite, nontronite, hectorite, saponite, and saucorite. Beneonite is especially preferred. Other suspending agents include cellulose deri~atives and polyvinyl alcohol.
~ The rate of application of the compounds of the invention will depend on a number of factors including, for example, the compound chosen for use, the identity of the plants whose growth is to be inhibited, the formulations selected for use and whether the compound is to be applied for foliage or root uptake.~ As a general guide, ho~ever, an applic~ion rate of from 0.0001 to 20 kilograms per hectare is suitable while from 0.001 to 10, for example 0.001 to 2 kilograms per hectare may be preferred.
The compositions of the invention may comprise, in addition to one or more compounds of the inven~ion, one or more compounds not of the invention but which possess biological activity. Accordingly in yet a still further embodiment the invention provides a herbicidal composition comprisin~ a W O 93/19S99 ~31~ ~ PCT/&B93/00542 ~ _ 18 -mixture of at least one herbicidal compound of formula (I) (IA) or (IB~ as hereinbefore defined with at least one other herbicide~
The other herbicide may be any herbicide not having the formula (I) (IA) or (IB). It uill generally be a herbicide having a complementary action in the particular application.
Examples of useful complementary herbicides include:
A. benzo-2,1,3-thiadiazin-4-one-2,2-dioxides such as bentazone;
B. hormone herbicides, particularly the phenoxy alkanoic acids such as MCPA, MCPA-thioethyl, dichlorprop, 2,4,5-T, MCPB, 2,4-D, 2,4-DB, mecoprop, trichlopyr, clopyralid, and their derivatives (eg. salts, esters and amides);
C. 1,3 dimethylpyrazole derivatives such as pyrazoxyfen, pyrazolate and benzofenap; :
D. Dinitrophenols and their derivatives (eg. acetates) such as dinoterb, ~;
dinoseb and its ester, dinoseb acetate;
E. dinitroaniline herbicides such as dinitramine, trifluralin, ethalflurolin, pendimethalin, oryzalin;
F. arylurea herbicides such as diuron , flumeturon, metoxuron, neburon, isoprot:uron , c~lorotoluron , chloroxuron, linuron, monolinuron, chlorobromuron, dai~uron, methabenzthiazuron;
G.~ pbenylcarbamoyloxyphenylcarbamates such as phenmediph~ and desmedipham;
H. 2-phenylpyridazin-3-ones such as chloridazon and norflura~sn;
I. uracil herbicides such as lenacil , bromacil and terbacil;
J. triazine h~rbicides such as a~razine , simazine, aziprotryne, cyanazine, prO~etryD, dime~hametryn, simetryne~ and terbutryn;
K. phosphorothioate herbicides such as piperophos, bensulide, and butamifos;
L. thiocarbamate herbicides such as cycloate, vernolate, molinate, thiobencarb, butyla~e , EPTC , tri-allate, di-allate, esprocarb, tiocarbazil, pyridaee, prosulfocarb and di~epiperate;
~. 1,2~4-triazin-5-one herbicides such as metamitron and metribuzin;
N. benzoic acid herbicides such as 2,3~6-TBA, dicamba and chloramben;
O. anilide herbicides such as pretilachlor, butachlor, alachlor, propachlor, propanil, metazachlor, me~lachlor, acetochlor , and dimetha~hlor;
P. dihalobenzonitrile herbicides such as dichlobenil, bromDxynil and ioxynil;
:

W~ 93Jlg59~ ~ ~1 3 ~?~ 7 ~ 6 PCT~G~93/~0~42 - 19 -Q. haloalkanoic herbicides such as dalapon, TCA and salts thereof;
R. diphenylether herbicides such as lact~fen9 fluroglycofen or salts or ester thereof, nitrofen, bifenox, aciflurofen and salts and esters thereof, oxyfluorfen, fomesafen, chlornitrofen and chlomethoxyfen;
S. phenoxyphenoxypropionate herbicides such as diclofop and esters thereof such as the methyl ester, fluazifop and esters thereof, haloxyfop and esters thereof, quizalofop and esters thereof and fenoxaprop and esters thereof such as the ethyl ester;
T~ cyclohexanedione herbicides such as alloxydim and salts thereof, sethoxydim, cycloxydim, tralkoxydim , and clethodim;
U~ sulfonyl urea herbicides such as chlorsulfuron, sulfometuron, me~sulfuron and esters thereof; benzsulfuron and esters thereof such as DPX-M6313, chlorimuron and esters such as the ethyl ester thereof pirimisulfuron and esters such as the methyl ester thereof, 2-[3-(4-methoxy-6-methyl-1,3,5- triazin-zyl)-3-methylure~dosulphonyl) benzoic acid esters such as the methyl ester thereof (DPX-LS300) and pyrazosulfuron;
V~ imidazolidinone herbicides such as imazaquin, imazamethabenz, imazapyr and isopropylammonium sal~s thereof, imazethapyr;
. arylanilide herbicides such as fl~mprop and e~ters thereof, ~ benzoylprop-ethyl9 difluf~nican X. anino acid herbicides such as glyphosate and glufosinate and their salts and esters , sulphosate (glyphosate trimesium) and bialaphos;
Y. organoars~nical herbicides such as monosodium methanearsonate (MS~A);
Z. herbicidal amide deri~ative such as napropamide, propyzamide, carbetamide, tebuta~t bromobutide, isoxaben~ naproanilide and naptal~m;
M triketones such as ~ulcotrione;
BB. ~iscellaneous herbicides including ethofum*sate, cinmethylin, d fenzoquat and salts thereof such as the methyl sulphate sal~, clomazone, oxadiazon, bromofenoxim, barban, tridiphane, flurochloridone, quin~hlorac and mefanacet;
CC. ~xa~ples of usefuI contact herbicides include:
bipyridylium herbicides such as those in which ~he active entity is paraquat and those in ~hich ~he active en~ity is diquat;

* Thes2 compounds are preferably employed in combination uith a ~ 20 -safener such as dichlormid.
** These compounds have been demonstrated to exhibit additive andin several instances synergystic effects when applied in admixture with compounds of the present invention.
It is an ad~antage of preferred compounds of the prPsent invention that they are compatible with a wide range of co-herbicides such as those listed above and may exhibit additive or synergystic effects in such mixtures.
The invention is illustrated by the following Examples.

The compounds listed in Table 1 were characterised by their NMR
spectrum. In each case, the moiety derived from monic acid A (i.e. the "normonyl" group of structure VI belou) ~as characterised by a complex but readily identifiable spectrum which corresponded to tha~ of Compound No 1, monic acid itself. Table II below lists the vis;ble characterising features of the spectrum a~tributable to the different groups R2 although key peaks derived from the monic acid moiety may be included for comparative identificaeion. The solvent in which the spectrum was recorded is also given.
TABLE II

Compound Solvent ~ NMR
Num~er 2 CDC13 5.9(1~9m); 5.2(2~ ; 4-6(2H,d) 3 d6-DNS0 4.0(2~,t); 3.5(2H,m~
4 C~C13 2.3(3~,s) CDC13 6.5(1H,t); 4.3(2~,m); 3.9(2~,m); 3.8(2~,m~
6 CDC13 400(2~,t); 2.2~3H,s) 7 CDC13 8.0-7.5(5H~m~, 4.2~2H~t~; 2.2S2H,t) 8 d6-DMS0 4.6t2H,s) 9 CDC13 4.8(28,s~
CDC13 7.7-7.4(4~,m); 5.2(2~,s) 11 CDC13 7.6-7.2~4H,m); 5.1(2H,s) 12 CDC13 7.3-7.1(4~,m); 5.1(2~,s); 2.2(3~,s) 13 ~DC13 7.4(4H,s); 5.1~Z~s~; 4.7(2~,d~

W O 93/19~99 PCT/GB93/00542 21 - ~ , 7 ~ ~
TABLE II (Continued) . ~
Compound So~ven~ 1~ NMR
Num~er 14 CDCl3 8.1-7.8(4H,m); 4.8(2H,d) `
d6-DMS0 10.2(1~,s); 9.8(1~,s); 7.9(1H,s); 7.2(1H,d);
6.6(1H~s) 16 CD~13 9.8(1H,s); 9.6(1H,s); 7.6(2H,d); 6.6(2~,d);
2.9(6~,s) 17 CD~13 4.1~2H,t); 3.4(2~,t) 18 CD~13 7.8(1~,s); 7.5(1H,s); 7~1~1H,d); 6.6(1R,s) 19 d6-~MS0 6.8(1~,s); 1.2(3H,t) CDCl3 4.1t2~;t) 21 CDC13 3 7(3~S) 22 CDCl3 8.0(2H,d); 7.8(2~,d); 7.6(1H,s) .

-This Exa~ple illustrates ~he preparation of 2-Vinyloxye~hyl monate A
(Compound No 5 of Table 1).
~ Sodium monaee A (lg~ ~mH~ uas dissolved in dimethylform~mide (25ml) and stirred ui~h 2-chloroethylvinyl e~her ~0.6ml9 6mM~, hexamethyl-phosphoramide (3 drops) and sodium iodide (0.9g~ at 80C for 6 hours.
:~fter evaporation i~ vacuo ~he residue was partitioned between ethyl acetate and bri~e, and the aqueous phase further extracted with ethyl acetate (3x50ml). The combined organic fractions ~ere uashed with 10%
sodium thiosulpha~e solueion9 saturated sodiu~ bicarbo~ate solution and brine~ dried ~MgS04) and evaporated in vacuo. Separation on silica (type 60, 20g) eluting ~ith 0 to 4Z me~hanol/CPOC13 gave the produc~, which crystallised on sta~ding to give a solid of melting point 78-80~Co The NMR
spectrum was as indicated irO Exa~ple 1.
EYA~LE 3 This Example illustrates the preparation of cyanomethyl monate A
(Compound No 9 of Table 1)~
A solution containing sodium monate A (2.00g, 5.4~mol)~
chloroacetonitrile (0.35ml, 5.4m~ol) and dimethylforma~i~e (50ml~ was stirred 1 hour at 80 and then evaporated in YacUO- The residue uas taken up in ethyl aceta~e, which uas washed uith aqueous sodium bicarbona~e and W O 93/19599 ~ 22 - PCT/GB93/~0542 then brine, dried (MgS04), evaporated in vacuo, and purified by chromatography (O to 4% methanol in chloroform, 20g silica gel) to give the desired product as a clear oil. The NMR spectrum ~as as indicated in Example 1.

This Example illustrates the preparation of 3-bromobenzyl monate A
(Compound No 11 of Table 1).
A solution containing sodium monate A (l.lgm 3mmol), m-bromobenzyl bromide (0.75g, 3mmol), and dimethylformamide (35ml) was stirred at 20C
for 5 hours and then evaporated in vacuo. The resiude was taken up in ethyl acetate/brine, the organic layer washed with aqueous sodium bicarbonate, then brine, dried (MgS04), evaporated in vacuo, a~d purified by chromatography (O to 6% metha~ol in dichloromethane, 20g silica gel) to give the desired product as a colourlass oil which solidified to yield white powder of melting point 91C-92~C. The NMR spectrum was as indicated in Example 1.

ThiS Example illustra~es the preparation of 3-methylbenzyl monate A
(Compound No 12 of Table l)o A solution containing sodium monate A (0.73g, 2mmol), ~-bro~o-m-xylene (0:37g, 2mmol) and dimethylformamide (25ml~ ~as stirred at 20C for 17 hours and then evaporated in vacuo. The residue was taken up in ethyl acetate/brine, the organic phase washed with aqueous sodium bicarbonate and then brine, dried (MgS04~ and evapora~ed in vacuo. The residual oil was purified by chromatography (O to 4X ~ethanol in dichloromethane7 15g silica gel) to yield the desired produc~ a3 a colourless oil. The N~R spectrum uas as indieated in Ex~mple 1.
EXA~PLE 5 ~:
This Example illustrates the preparation of 4-hydroxymethylbenzyl ~onate A (Compound No 13 of Table 1). ::
~ -Toluic acid (13.6g, lOOmmol~ was refluxed in methanol t95ml) and concentrated sulphuric acid (5ml~ for l~ hsurs. The reaction was evaporated to half volume, poured into water, extraeted with ethyl acetate, dried (M~S04), and eYaporated in vacuo. To the residue was added N-brcmosucc~nimide (17.8g, lOOmmol), benzoyl peroxide (lOOmg~ and earbon tetrachloride (50ml) and refluxed for 2* hours. The reaction was ~hen filtered, and the filtrate evaporated in vacuo.

- 23 - ~ ~3 7 ~ ~i The product, methyl-4~bromomethylbenzoate (9.2g, 40mmol) in toluene (80ml) was cooled to -303C and a solution of diisobutyl aluminium hydride in toluene ~60ml, 25%, BOmmol) was added dropwise and stirred for 1 h~ur.
The solution was allowed to warm to room temperature and stirred a further 2 hours. The reaction was then quenched with methanol, filtered, and the filtrate washed with aqueous sodium bicarbonate solution and then brine.
The orgnaic layer was dried (MgS04) and evaporated in vacuo to yield 4-bromomethylbenzyl alcohol.
A solution co~taining sodium monate A (4mmol) and 4-bromomethylbenzyl alcohol (4mmol~ in dime~hylformamide (60ml) was stirred overnight at room temperature, and then e~aporated in vacuo. The residue ~as taken up in ethyl acetate/brine, ~ashed with aqueous sodium bicarbonate and then brine, dried and evaporated. The residue was purified by chromatography, eluting with methanol~dichlorometha~e ~ixtures to yield a colourless oil. The NMR
spec~rum was as indicated in Example 1.

This ~xample illustrates the preparation of 4-dimethylaminobenzoyl-monhydrazide A (Compound No 16 of Table 1).
Monic acid A (3.44g, lOmmol~ ~as dissolved in tetrahydrofuran (lOOml) a~d cooled to O~C. Triethylamine (1.5ml, ll~mol) and isobutylchloroformate ~,4ml, llmmol) ~ere added and -~tirred for 30 minutes~ Dimethylamino-ben~ahydrazide ~1079g, ~Ommol~ ~as added and the reaction mixture stirred for 5 hours. The reaction mixture was then filtered and evapora~ed under reduced pressure. The residue was crystallised from ether to yield the de~ir~d product as a white ~olid of melting point 116-118C. The NMR
spec~rum ~as as indicated in Ex~mple 1.

This ~xample illusta~es the preparation of l-bromo-8-octyl monate A
(Compound No 17 of Table 1~.
A solution containing sodium monate A (l.OgJ 2.7m~ol) and 1,8-dibromooctane (0.75g, 2.7mmol) in dimethylformamide ~5ml) was stirred overnight at room temperature and then evaported under reduced pressure.
The residue was dissolved in ethyl acetate/~ater and the orga~ic layer washed ~ith water, dried (MgS04) and evapora~ed under reduced pressureO
The resulting residue was purified by column chromatography (silica gel, eluting uith O to 3X methanol in dichloromethane~ to yield the desired product as an oil. The NMR spectrum uas as indicated in Example 1.

W O 93/lgS99 - PCT/GB93/00542 ~ r~ 24 -The Example illustrates the preparation of cetyl monate A (Compound No 20 of Table 1).
Monic acid A (25.8g, 75mmol), potassium carbonate ~10.5g, 76mmol), sodium iodide (15.0g, lOOmmol) and cetyl bromide (45ml, 147mmol) were stirred in dimethylformamide (750ml) and hexamethylphosphoramide (150 drops) for 24 hours. The mixture was diluted with ethyl acetate (1.51), washed with water (4 x 0.51) and brine, dried and evaporated. The residue ~as purified on silica (1200g), eluting with 5~ methanol in chloroform, to give a fine white powder. This was recrystallised from ethyl acetate/hexane to give the desired product. The NMR spectrum was as indicated in Example 1.

This Example illustrates the preparation of pent-4-enyl monate A
(Compound No 25 of Table I).
Sodium monate A (160mg, 0.44mM) was dissolved in dimethylformamide (2ml) and stirred ui~h 1-bromopent-4-ene (131mg, 0.88~M~ and N,N-dimethylpro wleneurea (0.38ml) at room te~perature for 4 hours and ehen at 70C for 2 hours. Volatile components ~ere removed by evaporation in vacuo. Separation on silica eluting with 55:45 acetoneJhexæne gave the de~ired product as a colourless syrup.
1~ NMR ~tCDC13) 5.82~ m), 5.77 (lH, S)7 5.08 (1~, d), 5.00 (1~, d), 4.11 (2H~ t), 2.21 ~3~, s), 1.22 (3~, d~, 0.95 ~3~, d).
; EXAMPLES 10 T0 15 The following compounds were prepared using the general method of Examplè 9:
4-Methoxybenzyl monate A (Compound ~o 55 of Table I~
NMR ~(CDC13) 7.3~ (2~, d), 6.88 (2HI d), 5.79 (lH, s), 5.07 (2H, s), 3.90 (3H, s)~ 2.21 (3~, s), 1.22 (3H, d3, 0.92 (3~, d).

3-Nitrobenzyl monate A (Compo~nd No 70 of Table I) H NMR ~(CDC13) 8.28 (1~, s), 3.20 (lH, d~, 7.70 (1~, d~, 7.54 (lH, t), 5.80 ~2H, s), 2.22 (3~, s), 1.21 (3~, d), 0.93 (3~, d).

Propargyl monate A (Compound No 71 of Table I~
~ NMR ~(CDC13) 5.80 (lH, s), 4.71 (2H, s), 2.22 (3~, s)~ 1.21 (3~9 d), 0.94 (3H, d).

W O 93/195~9 ~ ~ 3 i 7 ~ ~ PCT/GB93/00542 Ethyl acet-2-yl monate ~ (Compound No 72 of Table ~) -'~ NMR ~(CDCl3) 5.89 ~lH, s), 4.63 (2H, abq), 4.22 (2H, q), 2.22 i~, s), 1-29 (3~9 t), 1.22 (3~, d), 0.91 (3H, d).

Decyl monate A ~Compound No 73 of Table I) 1~ NMR ~(~DCl3) 5.78 (lH, s), 4.Q8 (2~, t), 2.21 (3H, s), 1.21 (3H, d), 0.95 (3H, d), 0.87 (3H, t).

2-Phenoxyethoxy monate A (Compound No 27 of Table 1) 1H NMR S(CDC13~ 7.29 (2~, t), 6.91 (3~, m), 5.81 (1~, s) 4.46 (3H, t), 4.19 (3H, t), 2.22 (3~, s), 1.21 (3H, d), 0~92 (3H, d).

This ~xa~ple illustrates the preparation of prop-2-yl monate A
(Compound No 36 of Table I).
Sodium monate ~ (200mg, 0.55mM) was dissolved in dimethylformamide ~2ml) and stirred with 2-bromopropane (136mg, l.llmM), N~N-dimethylpr~pyleneurea (0.476g) and sodium iodide (166mg, l.llmM~ at room ~emperature for 1.5 hours and then let to stand for 4 days. Volatile components were re~oved by evaporation in vacuo. Separa~ion on silica eluting ~ith 55:45 acetone/hexane ~ave the desired product as a colourless sy~up.
1~ NMR ~(CDCl3) 5.72 (1~, s~, 5.02 ~1~, m), 2.21 (3H, s), 1.24 (6H, d), 1.22 ~3~, d), 0.94 (3~, d).
~n~s 17 ro 19 The following compounds ~ere prepared in a manner corresponding to that to Example 16:-2-E~boxye~hyl monate A (Compound No 26 of Ta~le I~
~ NMR ~(CDC13) 5.81 (1~, s), 4.26 (2H, t), 3~66 (2~, t), 3.54 (2~, t), 2.21 (3~, s), 1.22 (3~, m), 1.21 t3H, d), 0.94 ~3~, d).

Pent-4-ynyl monate A (Compound No 31 of Table I) lH NMR ~CDCl3~ 5.78 (lH, s), 4.20 ~2H, t), 2.21 (3~, s)~ 1.22 (3~, d), 0.94 (3H, d3.

Ethyl propion-2-yl monate A (Compound No 45 of Table I~, obtained as a mixture of diastereoisomers.
1~ NMR ~(CDCl3) 5.86 (1~, s), 5.09 (1~, m), 4.21 (2H, q), 2.21 (3H, s), ~ ~.3 ~ 26 - P~T/GB93/~0542 1.50 (3~, d), 1.25 (3H, t), 1.22 (3~, d), 0.92 (3~, d~.

This Example illustrates the preparation of 2-(4-chlorophenoxy)ethyl monate A (Compound No 28 of Table I) Monic acid A (200mg, 0.58mM) was dissolved in dimethylformamide (lml) and stirred with 2-(4-chlorophenoxy)ethyl bromide (273mg, 1.16mM) and N,N-dimethylpropyleneurea (510mg, 3.98mM). Potassium carbonate t120mg, 0.87~M) was added and the mixture stirred at room temperature for 1 hour and at 80C for 1.5 hours. Volatile componenes were removed by evaporation in vacuo. Separation on silica eluting with 55:45 acetone/hexane gave the desired product as a gum.
B NMR ~(CDC13) 7 25 (2H, d), 6.82 (2H, d), 5.80 (lH, S)9 4.40 ~2H, m), 4.16 (2~,~m), 2.22 (3B, s), 1.21 (3H, d), 0.93 (3~, d).
E%AMPLES 21 T0 32 The following compounds were prepared using the general method of Example 20:
2-((2-methoxy)ethoxy)ethyl monate A (Compound No 42 of Table I) H NHR ~(CDCl3) 5.81 (1~, s), 4.27 (2~, t), 3.72 (2~, t), 3.65 (2~, m), .
~ 3.55 (2H, m), 3.40 (3~, s), 2.21 (3~, s), 1.21 (3H, d), 0.95 (3H, d).
:
A ~1:4~ mixture of 1-methylprop-2-enyl mona~e A (Compound No 49 of Table I
- its~lf a mixture of diastereoisomers) and but-2-enyl monate A (Compound ~o 48 of Table I - itself a mixture of geometric~l isomers) 1-~ethylprop-2-enyl monate A
1~ N~R ~(CDCl3) 5.78 (lH, m), 5.39 ~1~, m), 5.25 ~1~, m), 5.15 (lH? m), 2.21 ~3~, s), 1.70 (3H, s), 1.21 ~3H, d), 0.99 and ~.80 (3~, 2xd).

But-2-enyl monate A
~ ~MR ~(CDC13~ 5.78 (lH, m), 5.60 (1~, m~, 4.63 and 4.52 (2~, 2xd), 2.21 (3H, s), 1.21 (3H, d), 0.95 (3~, d).

2-(Ethoxycarbonylmethoxy)ethyl monate A (Compound No 30 of Table 1) lH NMR ~(CDCl3~ 5.80 (1~, s), 4.29 (2~, t), 4.23 (2H9 q), 4.14 (2~, s), 3.80 (2B, t), 2.23 (3H, s), 1.28 (3H, t), 1.23 (3~, d), 0.94 (3H, d~.

93~19~9g ~ 7 ~ PCT/GB93J00542 2-(Acetoxy)ethyl monate A (Compound No 29 of Table 1) lH NMR ~(CDCl3) 5.78 (lH, s)? 4.28 (4H, s), 2.23 (3~, S)9 2.08 (3H, s), 1.22 (3~, d~, 0.94 (3H, dj.

2-(Car~amoylmethoxy)ethyl monate A (Compound No 46 of Table 1) 1~ NMR ~(C~C13) 6.65 (lH, s), 6.50 (lH, s), 5.86 (1~, d), 4.54 (2H, s), 2.22 (2H, s), 1.21 (3H, d), 0.92 (3~, d3.

3-Chloroprop-2-en-1-yl monate A (Compound No 47 of Table 1) 1~ NMR ~(CD~13) 6.37-5.91 (2H, m~, 5.79 (1~, s), 5.81 & 4.59 (2~, 2 x d), 2.21 (3~, s), 1.22 (3~, d), 0.94 (3~, d).

Ethyl monate A ~Compound No 35 of Table 1) NMR ~(CDCl3) 5.75 (lH, s), 4.12 (2H, q), 2.21 ~3H, s), 1.29 ~3H, t~, 1.21 (3~, d), 0.93 (3H, d).

Butyl monate A ~Compound No 37 of Table 1) 1~ NMR ~(CDC~3) 5.75 (1~, s), 4.10 (2~, t), 2.20 (3~, s), 1.65 (2~, m), 1.38 (2~, m), 1.21 t3~, d), 0.92 (6~, m).

~yelohexyl mona~e A (Compound Mo 39 of Table 1) :: :
H NHR ~(CDCl3) 5.73 (1~, s), 4.78 (lH, m), 2.21 ~3~, s), 1.80-1.20 -~
~10~, s~ 22 (3~, d), 0.94 (3~, d).

~thoxy~ethyl monate ~ (Compound No 76 of Table 1).
1~ NMR ~(CDCl3) 5.79 (1~, s), 5.30 (2~, sj, 2.22 (3~, S)9 1.22 (3H, d), 0.92 (3B, d).

: EXAMPLE 33 This Example illustrates the preparatio~ of 2-(allyloxy)ethyl monate A
(Compound No 23 of Table I) .
S~age 1 Preparation of l-Mesyloxy-2-allyloxyethane 2-Allyloxyethanol (5.0g, 49mM) uas stirred with trie~hy~amine (5.2g, 51mM) in dichloro~etha~e (25ml3 at 0C under nitrogen. Methanesulphonyl rhloride (5.61g, 49mM) was added slowly with stirring. The cooling bath was removed at the mixture stirred at room temperature for a further 1 hour. Yolatile components were removed by evaporation in vacuo. The 93/19599 ~, PCTJGB93/00542 ~ 28 -residue was partitioned between diethyl ether and water. The organic fraction was washed twice with water and once uith brine, dried (MgS04) and evaporated in vacuo. The product was a yellow oil.
Stage 2 Preparation of 2-(allyloxy)ethyl monate A
80dium monate A (165mg, 0.45mM) was dissolved in dimethylformamide (2ml) and stirred with 1-mesyloxy-2-allyloxyethane (162mg, 0.90mM) and N,N-dimethylpropyleneurea (0.39ml) at room temperature for 19 hours.
Volatile components were removed by evaporation in vacuo. Separation on silica eluting with 55:45 acetone/hexane gave the desired product as a colourless oil.
~ ~MR ~(CDC13) 5.gO (1~, m), 5.81 (1~, s), 5.27 (lH, d), 5.20 (lH, d), 4.27 (2~, t), 4.05 (2~, d), 3.75 (2~, t), 2.21 (3~, s), 1.22 (3H, d), 0.92 (3H, s)~

The following compounds were prepared using ~he general method of Example 33:-3-Yinyloxypropyl ~onate A (Compound No 33 of Table 1) 1~ NMR ~(CD~13) 6.46 (lH, dd), 5.76 (lH, s), 4.19 (3H, m), 4.01 (1~, dd~, 3.79 (2~, t), 2.21 (3~, s3 ? 1.23 (3~, d), O.9S ~3H, d)~

2~(3-Chloroprop-2-en-1-yIoxy)ethyl monate A No 44 of Table l) 1~ NMR ~CDCl3) 6.20 ~1~, d), 5.95 (1~, q), 5.81 (1~, s), 4.27 (4~, m), 3.70 (2~, t~t 2.22 (3~, s), 1.22 (3H, d), 0.94 (3~, d3.

4-Vinyloxybut-1-yl monate A ~Compound No 32 of Table l) lH ~M~ ~(CDCI3) 6.46 (1~, abq), 5.74 (1~, s), 4.11 (2L, m~, 2.21 (3~, s), 1.20 ~3Ht d)7 0.92 (3~9 d).

2-1prop-2-yn-1-yloxy)ethyl monate A (Compound No 43 of Table l) ~ R ~(CDCl3) 5.80 (1~, s), 4.28 ~2~, t), 4.21 (Z~, d), 3.79t2H, t) 2.48 (1~, t), 2.21 (3~, s), 1.21 (3L, d), 0.94 (3~, d~

This Example illustrates the prepara~ion of N,N-Die~hyl-monicamide A
(Compound No 63 of Table I) Monic acid A (200mg, 0.58mM) was dissolved in tetrahydrofuran (5ml) and cooled to -10C u~der nitrogen. Triethylamine (59mg, 0.58mM) and i~obutylchloroformate (80mg, 0.58mM~ uere added and s~irred for 30 minutes.

93/19599 ~ 3 7 ~ g3 A solution of diethylamine (47mg, 0.58mM) in tetrahydrofuran (0.5 ml) was added an the reaction mixture stirred for 1 hour and ~hen at room temperature for 2 hours. The reaction mixture was filtered and evapora~ed in vacuo. Thin layer chromatography indicated that the reaction was incomplete so further diethylamine (20mg) in tetrahydrofuran (3ml) was added and the mixture stood at room temperature overnight. Volatile components were removed by evaporation in vacuo. The residue was taken up in water (lOml) and extracted with chloroform (3xlOml). The combined organic extracts were dried (HgS04) and evaporated in vacuo. The resulting residue was purified by column chromatography (silica gel? eluting with methanol/chloroform 1:9) to give the desired product as a colourless gu~.
H NMR ~(CDC13) 5.87 (1~, s), 1.91 (3~, s), 1.21 (3H, d), 1.12 (6H, m), 0.92 (3~, d).

The following compound was prepared using the general method of Example 38: -Monic acid A morpholine amide (Compound No 64 of Table I) H NMR 8(CDC13) 5.81 (1~, s), 3.67-3.47 (8H, m), 1.90 (3~, s), 1.21 (3~, d), 0.94 (3H, d).

N-C2,4-Dichlorophenyl)-N-methyl~onic amide A (Compound No 60 of Table 1) H ~MR ~(CDC13) 7.50-7;.15 (3H, m), 5.49 (1~, s), 3.20 (3~, s), 2.18 (3~,~s), 1.22 ~3L, d),~O.95 (3H, d~. ;

N-(2-~ydroxyethyl)monica ide A (Co~pound No 77 of Table 1).
H NMR~ d6-DMSO) 7.89 (1~, t), 5.81 (1~9 5)9 4.51 (4H, m~, 2.21 (3H, s), 1.21 (3H, d), 0.95 (3H, d).

N-(2-Ethoxyethyl)monicamide A (Compound No 78 of Table 1).
1~ NMR ~(d6-DMSO) 6.21~(lH, ~), 5.68 (1~, s), 3.62-3.42 (6H, m), 2.20 (3H, s), 1.20 (6~, m), 0.92 (3H, d).

N-(Ethoxycarbonylmethyl)mo~icamide A (Compound No 66 of Table 1) 1~ NMR ~(CDC13) 6.24 ~lH, t), 5.73 (1~, s), 4.23 (2~, q), 4.06 (2~, d), 2.19 ~3H, s), 1.30 (3H, t), 1.22 (3H, d), 0.92 (3~, d).

Monicamide A (Compound No 61 of Table 1) lH NMR ~(d4-MeO~) 5.93 (1~, s), 2.29 (3~, s), 1.35 (3~, d), 1.10 t3~, d).

~3~ 9 - 30 -N-(2,4-Dichlorophenyl)monicamide A (Compound No 58 of Table 1) lH NMR ~(d4-MeOH) 7.99 (lP., d), 7.63 (lH, d), 7.45 (1~ dd), 6.20 (lH, s~, 2.38 (3H, s), 1.33 (3H, d), 1.10 (3H, d).

N,N-bisallylmonicamide A (Compound No 79 of Table 1).
1~ NMR ~(CDC13) S.89 (~H, s), 5.76 (2H, m), 5.16 (4H, m), 1.97 (3H, s), 1.22 ~3~, d), 0.93 (3H, d).

Monic acid A piperidine amide (Compound No 80 of Table 13.
H NMR ~(CDC13) 5.81 (lH, s3, 3.50 (4H, m), 1.85 ~3H, s), 1.60 (6H, m), 1.21 t3H, d), 0.92 (3H, d).
. :.
Monic acid A N-methylpiperazine amide (Compound No 81 of Table 1).
H NMR ~(d4-MeO~) 5.99 (lH, s), 3.72 (4~, m), 2.56 ~4H, t), 2.44 (3H, s), 1.97 ~3H, s), 1.32 (3~, d), 1.06 (3H, d). ~:~
,, NrN-Dimethylmonichydrazide A (Compound No 82 of Table 1).
1~ NMR ~(CD~13) 5.52 (lH, s), 2.40 (6~9 s), 2.04 (3H, s), 1.10 (3H, d), :::~0.83 (3H, d).

Mo~ichydrazide A (Compound No 65 of Table 1) -~
~: H N~R ~(d4-MeQH) 5.80 ~(lH, s), 2~28 (3~, s), 1.30 (3H, d), 1.04 (3H, d).
'::
N-(Prop-2~ylidiene)~onichydrazone A (Compound No ~3 of Table 1).
1~ NMR ~(d4-MeOH) 6.84 (1~, s), 5.76 ~lH, s), 2.33 (3H, s), 2.20 (3H, s), 2.12 (38, s), 1.35 (3~, d), lolO (3~, d).

: N-~2,5-Dichlorophenyl)monicamide A ~Compound No 59 of Table 1) ~H ~MR ~(d6-DMSO) 9.42 (lH, s), 7.86 (lH, d), 7.46 (lH, d), 7.18 (lH, dd), ::~

6.05 (1~, s~, 2.21 (3~, s), 1.02 (3H, d), 0.80 t3H, d).

Monic acid A pyrrolidine amide (Compound No 84 of Table 1).
H NMR ~(CD~13~ 5.8B (lH, s), 3.4~ (4~, m), 2.08 (3H, s), 1.90 ~4H, m), 1.21 (3H, d3, 0.92 (3~, d).

W O 93/1959g ~ 7 il ~ PCT/~B93/00542 Monic acid A 2,6-dimethylmorpholine amide (Compound No 85 of Table 1).
lH NMR ~(CDCl3) 5 80 (lH, s), 3.50 (6H-, m), 1.85 (3B, s), 1.20 (9H, m), 0.93 (3H, d).

N-Allylmonicamide A ~Compound No 86 of Table 1).
NMR ~(CDC13) 5.92-5.72 (2~, m), 5.68 (lH, s), 5.22-5.10 ~2~, m), 3.10 (2H, m), 2.18 (3~, s), 1.21 (3~ d), 0.92 (3H, d).

N,N-bis(2-hydroxyethyl)monicamide A (Compound No 87 of Table 1~.
H NMR ~(d6-DMS0) 5.90 (1~, s), 3.40 (4~, m), 3.30 (4~, m), 1.80 (3H, s), 1.10 ~3~, d), 0.78 ~3H, d) This Example illustrates the prepara~ion of S-(carbometh~xymethyl) thiomonate A (Compound No 75 of Table I).
ffonic acid A (80mg, 0.23mM) was dissolved in tetrahydrofuran ~3ml) and cooled to -10C under nitrogen. Triethylamine (24mg, 0.23mM~ and a solution of isobutylchloro~ormate (32mg, 0.232M) in tetrahydrofuran ~0.7ml) were added and stirred for 20 minutes. A solution of me~hylthioglycolate ~25mg, 0.23mM~) in tetrahydrofuran (0.5 ml) was added an the reaction ~:
mixture stirred for 1 hour and then at room temperature ~cr 3 hours. The . , reactlon mixture was evaporated in vacuo and the resulting residue stored at room temperature for 7 days. The mixture was purified by column chromatography ~silica gel, eluting ~ith methanol/chloroform 1:9) to give the desired product as a colourless gum (67 m~, 67~
N~R ~CD~13) 6.10 ~ 9 S~ 4.76 ~3~, s), 4.74 (2~, s~ 2.21 (3~, s), 1.22 (3~, d), 0.93 (3~:d).
EgAHPLES 58 AND 59 The following compounds were prepared using the general method of Example 57.

S-Phenylthiomonate A (Compound No 74 of Table 1~
1~ NMR ~(CDCl3~ 7.42 (~H, s3, 6.18 (l~ s), 2.20 (3~, S)7 1.22 (3~, d), 0.92 (3~, d).

S-(2-Yinyloxye~hyl)thiomonate A (Compound No 68 of Table 1~
1~ NMR ~(~D~13) 6.45 (1~, dd), 6.07 (1~, s), 5.80 (2H, s), 3.18 ~2a, t), 2.21 (3H, s), 1.73 (2~, t), 1.21 (3~, d), 0.95 (3~r d~.

W O 93/1g5g9 - PCTlGB93/00542 This Example illustrates the preparation of 3-Nitrophenyl monate A
(Compound No 52 of Table 1).
Monic acid A (200mg, 0.58mM) was dissolved in tetrahydrofuran ~5.5ml) and cooled to -10C under nitrogen. Triethylamine ~59mg? 0.58mM) and isobutylchloroformate (80mg, 0.58mM) were added and stirred for 10 minutes -and then at room temperature for 1 hour. Solids were removed by filtration and the filtrate con~entrated in vacuo. The residue was taken up in dichloromethane (2.5ml) and 3-nitrophenol (323mg, 2.32mM) added. A
solution of pyridine (35mg) in dichloromethane (0.5ml~ was added to give a clear homogeneous solution and the mixture was stirred at room temperature overnight. Solvents were removed ~n vacuo and separated on silica elu~ing with 55:45 acetoneJhexane to give the desired product.
, '~ NMR ~(CDC13) 8.10 (lH, d~, 8.02 tlH, m), 7.54 (1~, t), 7.47 tlH, d), 6.02 (lH, S)9 2.19 (3~, s), 1.22 (3~, d), 0.95 (3H, d~. -The following compounnds ~ere preared using th~ general method of ~xample 60:
: : .:
Phenyl monate A (Compound No 50 of Table 1) NHR~(CDC13) 7.~39 ~2~, t), 7.21 (lH, t37 7.10 (2H, d), 6.00 (lH, s), 2.28 (3~, s), 1.21 (3H, d), 0.93 (3~, d).

Purfuryl mon te A (CoMpo~nd No 56 of Table 1~
NMR ~(C~C13~ 7.42 (1~, s), 6.41 (1~, d)9 6.32 (1~, t), 5~79 (lH~ s), 5.08 (2~, s), 2.22 (3~, s)~ 1.21 (3~, d), 0.94 (3M, d).

Neopentyl monate A (Compound No 38 of Table 1) NMR ~(CDC13) 5.78 ~lH, s), 3.79 (2H, s)y 2.21 (3H, s)~ 1.21 (3H, d), 0.95 (12~, m).

2-Chloroethyl monate A (Compound No 57 of Table 1) H NMR ~(CD~13) 5.81 (1~, s), 4.37 (2H, t), 3.72 (2~, t~, 2.24 (3H, s), 1.22 (3H, d), 0.98 (3~9 d).

4-Methoxyphenyl monate A (Compound No 53 of Table 1~
H NMR ~(CDC13) 7.01 (2~, d), 6.88 (2H, d), 5.97 (lH, s), 3.80 (3H, s), 2.26 (3H, s), 1.22 (3~, d), 0.94 (3H, d).

33 ~ ~ ~ 3 7 ~

4-Chlorophenyl monate A (Compound No 51 of Table 1) lH NMR ~(CDC13) 7.28 (2H, d), 6.97 ~2~, d), 5.91 (lH, s), 2~20 (3H, s), 1.15 (2H, d), 0.88 (2H, d).

2-(Vinylthio)ethyl monate A (Compound No 67 of Table 1) H NMR ~(CDC13) 6.33 (lH, dd), 5.78 (1~, s), 5.28 (1~, d), 5.20 (lH, d), 4.28 (2H, t), 2.95 (2~, t), 2.21 (3~, s), 1.21 (3~, d), 0.95 (3H, d).

The following Example illustrates the preparation of Monic acid A
trimethylsulphonium salt (Compound No 88 of Table 1).
Trimethylsulphonium iodide t59mg, 0.29mM) was dissolved in water (5ml) and treated with Dowex lX2 (HO ) resin for 10 minutes. The solution was filtered into a solution of monic acid A (lOOmg, 0.29 ~M) in water (lOml)~
The solution was freeze-dried to give the desired product.
lH NMR ~(D20) 5.70 ~1~, s), 2.83 (9~, s), 1.90 (1~, s), 1.16 (3H, d), 0.91 (3H, d~.-The following Example illustrates the preparation of ~-4-(Methoxycarbonyl~phenyl monate A (Compound No 54 of Table 1).
~ Monic ac~d A (250mg, 0.72mM) ~as dissolved in dichloromethane (3ml). A
solution of triethylamine~(74mg, 0.73mM) in dichloromethane (lml) was added and the mixture stirred at room temperature for S minutes. The reaction mixture was cooled in an ice/~ater bath and a solution of isopreny}chloroformate (88mg, 0.73m~) in dichloromethane (lml) added slowly and the ~ixture stirred~with cooling for a further 10 minutes.
4-~Methoxycarbonyl)phenol (166mg, 1.09mM) and N,N-dimethylaminopyridine (9mg) were added and~the mixture stirred for a fur~her 2 hours with cooling. The crude reaction mixture was separated on silica eluting with 55:45 acetone~hexane to give the desired product.
1~ NMR 8(CDC13) 8.08 (2~, d), 7.18 (2~, d), 5.99 (1~, s)~ 3.91 (3~, s), 2.27 (3~, s), 1.21 (3~, d), 0.93 (3H, d).

The ollowing Example illustrates the preparation of 2-Vinyloxyethyl pseudomonate A (Compound No 89 of Table 1).
Pseudomonic acid A (200mg, 0.40mM) was dissolved în acetone (2ml) and stirred with l-chloro-2vinyloxyethane (85mg, 0.60mM~ and sodium iodide (132mg, 88mM). Potassium carbonate ~83mg, 0.60mM) ~as added and the W O ~3/l9599 PCT/GBg3~00542 ~ '`3 mixture stirred at room temperature for 2 hours and at reflux overnight.
Volatile components were removed by evaporation in vacuo. The residue was taken up in dimethylformamide (lml) and N,N-dimethylpropyleneurea (0.5ml) and heated at 80C for 4 hours. Further portions of 1-chloro-2-vinyloxyethane (85mg, 0.60mM) and sodium iodide ~120mg) were added and heating continued for 8 hours. The reaction mixture was ~-partitioned bet~een water and diethylether and the organic layer was washed with water and brine and then dried over magnesium sulphate. Separation on silica eluting with 55:45 acetone~hexane gave the desired product as a gum.
~ NMR ~(CDC13) 6.49 (lH, m), 5.76 (1~, s), 4.32 (2~, t), 4.20 (~, dd), 4.Q8 (2H, t), 2.32 ~2~, t), 2.20 (3~, s), 1.21 t3~, d), 0.95 (3~, d).
E ~ PLES 71 AND 72 The fsllowing compounds were prepared using the general method of Example 7Q:

Ethyl pseudomonate A (Compound No 90 of Tab}e 1).
~ NMR ~(CDC13) 5.79 (lH, s), 4.15 (2~, q), 4.11 (2~, t), 2.28 (2~, t), 2~21 (3~, s), 0.95 (3~ d3.

2-~ydroxyethyl pseudo~onate A (Comp~und No 91 of Table 1).
~ NNR ~(CDC13) 5.78 (1~, s), 4.21 (2H, t~, 4.08 (2H, t), 2.32 (2H, t), 2.21 (3X, s~, 1.21 ~3H, d), 0.95 (3H, d).
E8AHPLE_73 The foll~wing Example illustrates the preparation of N,N-Diethyl pseudomonicamide A (Compou~d No 92 of T ble 1).
Ps~udomonic acid A (200mg, 0.40mM~ ~as dissolved in tetrahydrofuran (4ml) and cooled to -10C under nitrogen. Triethylamine (41mg, 0.40mM) and isobutylchloroformate (5Smg, 0.40mM3 were added and stirred for 30 ~inutes.
A solu~ion of diethylamine ~32mg, 0.40mM) in tetrahydrofuran (2ml) was added an the reaction ~ix~ure stirred for 30 minutes and then stood at room temperature overnight. The reaction mixture was filtered and evaporated in vacuo. The residue ~as taken up in water (lOml) and ex~rac~ed with chloroform (3xlOml). The combined organic extraces were dried over magnesium sulphate and evaporated in vacuo. The resulting residue was purified by column chromaeography (silica gel, eluting with acetoneJhexane 55:45) to give the product as a colourless gum.
1~ NMR ~(CDC13) 5.78 (1~, s), 4.08 (2H, t~, 3.31 (4~, q), 2.28 (2~, t), 2.21 (3~, s), l.Z2 ~6~, t), 0.95 (3H, d).

W O 93/19599 ~ 7'1 ~; PCT/GB93/00542 - 35 _ This example illustrates the preparation of monic acid A .
isopropylamine salt (Compound No 96 of Table 1) ~`
Monic acid A (50mg, 0.15mM~ was dissolved in tetrahydrofuran (2ml3 and was treated with isopropylamine (8.6mg, 0.15mM). After 20 minutes at room temperature, a precipitate formed which was collected by filtration to give the desired product.
lH NMR ~(CDCl3) 5.76 (1~, s), 2.21 (3H, s), 1.21 (3H9 d), 1.10 ~6~, d), 0.93 (3H, d)-EXAMPLES 75 AND 76 .
.
The following compounds were prepared using the general method of ~Example 74: .

Monic acid A triethylamine salt (Compound No 97 of Table 1) 1~ NMR ~(CDC13) 5.B0 (lH, s), 2.88 (6H, q), 2.13 (3~, s3, 1.20 ~12H, m), 0.92 (3~, d).

Pseudomonic acid A triethylamine salt (Compound No 98 of Table 2) ~
H NMR ~(CDC13) 5.78 (lH, s), 4.08 ~2~t t), 3.00 (6~9 q), 2.21 (3H, s), 1.25 (9~t t), 0.94 (3H, d)~

This Example illus~rates the preparation of Monic acid A sodium salt (Compound No 99 of Table 1) Monic acid A (1.2g, 3.48mM) was suspended in water (35~1) and was treated ~ith an aqueous O.lM solution of sodium hytroxide (34r8ml, 3.48mN~.
The solution was freeze dried to give the desired produc~ as a white solid.
1~ N~R ~(D20) 5.69 (lH, s~, 1.85 (l~, s), 1~15 (3~, d), 0.90 (3H, d).
EXA~PLE 78 .
: This Example illustrates the preparation of 2-ethoxyethyl monate C
(Compound No la8 of Tab~e 3? from monic acid C (~ompound No 107 of Table 3) ~ onic acid C (1.62g, 0.49mM) was taken up in a mixture of dimethylformamide (lml) and N,N-dimethylpropyleneurea (0.43ml). Potassium ca~bona~e (0.102g, 0.74mM) was added and the reaction mixture stirred for 1 hour at 80-90CC. After cooling to room temperature, a solution of 2-chloroethylethylether (0.107g, O.99mM~ in dimethylformamide (0.5ml) was added and the mixture stirred at room temperature for 19 hours, at 90C for 6 hours and then lef~ to stand at room temperature overnigh2. Volatile components were remo~ed in ~acuo and the residue separated on silica1 ~j~ 3 36 - PCT/GBg3/00542 eluting with acetone/hexane ~1:1) to give the desired product as a gum.
1~ NMR ~(CDCl3) 5.81 Sl~, s), 5.45 (2H, d), 4.25 (2H, t), 3.75 (2~, t), 2.22 (3H, s), 1.23 ~3H, t), 1.17 (3H, d), l.00 (3H, d).
E~AMPLES 79 T0 87 The fol~owing compounds ~ere prepared using the general me~hod of :
Example 20:-2-(Hex-2-en-1-yl)ethyl monate A ~Compound No 94 of Table 1) H NMR ~(~DC13) 5.80 (lH, s), 5.30-5.60 (2H, m), 4.22 (2~, t), 2.21 (3~, s), 1.21 (3~, d), 0.95 (6H, m).
~:
Cyclopropylmethyl monate A (Compound No 93 of Table 1) :~
1~ NMR ~C~Cl3) 5.80 (1~, s), 3~92 (2~, d), 2.23 (3~, .c), 1.23 (3H, d), .
0.94 (3~, d), 0.57 (2~, m~, 0.29 (2~, m).

(E/Z) 2-(Prop-1-en~l-yloxy)ethyl monate A (1:1) (Co~pound No 24 of Table 1 1~ NMR ~(CDC13) 6.24 and S.79 (1~, 2 x d), 5.80 S1~, s), 4.81 and 4.44 , 2 x m),4 26 (2~, m),:2.23 (3L, s), 1.23 (3d, d), 0.95 (3~, d)~

2-(Prop-2-yloxy)ethyl monate A ~239075) (Compound No 100 vf Table 1) N~R~ ~CDCl3~ 5.Bl lld, s), 4.22 (2H, m), 3.63 (2H, t), 2.22 (3H, s), 1.:Z3 (3H, d), 1.18 (6B, d), 0.95 (3~, d).

2-Hethoxyethyl monate A (Co~pound No 101 of Table 1) ~ NMR ~(CDC133 5.83 (1~, s)~ 4.25 (2H, t), 3.60 (2B, t), 3.40 ~3H, s~, 2.22 (3~, s), 1.23 ~3H, d3, 0.95 (3~, d).
:: :
2-(Prop-1-yloxy)-ethyl monate A (Compound No 102 of Table 1), a mix~ure of diastereo~somers lH NMR ~(CDCl3) 5~80 (lH, s), 4.23 t2H, t), 3.65 (2~, t), 2~21 (3H, s~, 1.60 (2H, t), 1.21 (3~, d), 0.90 (6~, m).

2-Ethoxy-1-methylethyl monate A ~Compound No 103 of Table 1~ -~ NMR ~(CDCl3) 5.78 (1~, s), 5.09 (lH, m), 2.21 ~3~ s~, 1.20 (9H, 0), 0.93 ~3H, d).

W O 93/19599 ~ PCT/GB93/00~42 2-Cyclopropyloxyethyl monate A (Compound No 104 of Table 1) H NMR ~CDC13) 5.81 (lH, s), 4.21 (2~, t), 3.72 (2~, t), 2.21 (3H, s), 1.21 (3~, d), O.9S (3~, d), 0.60 (2~, m), 0.50 (2H, m).

2-Ethoxy-2-methylethyl monate A (Compound No 105 of Table 1), a mixture of diastereoisomers. ~lH NMR ~(CDCl3) 5.68 (lB, s), 4.02 (2H, t), 2.21 (3H, s), 1.15 (6~7 m), ~:
0.88 (6~, m).

The follouing compounds were prepared using the general method of Example 60.

A (5:2) mixture of i) 2-(hex-1-en-1-yloxy)ethyl monate A (Compound No 34 of Table 1) lH NMR ~CDGl3) 5.91 (1~, d), 5.79 (lH, s), 4.38 (lH, q), 2.20 (2H, s), 1.21 (3~, d), 0.92 (3~, d).
and ii) 2~ (vinyl~-but-1-yloxy)ethyl monate A (Compound No 95 of Table 1) : ~ N~R ~(CDC13) 5.79 (1~, s), 5062 (1~, m), 5.20 ~lH, d), 2.20 (2H, s), 1.21 ~3~, d), 0.92 (3H, d).
EXAMPLES 89 ~ND 90 : The follo~ing co~pounds ~ere prepared using the general method of Example 38:

N-Methoxymnnicamide A (Compound No 106 of Table 1) 1~ NMR ~(d6-DMS0) 5.58 (1~, s), 3.70 (3H, s), 2.20 (3~, s), i.21 ~3~, d), 0.95 (3H, d).

N-Ethylmcnicamide A (Co~pound No 62 of Table 1) H NMR S(CDC13~ 5.64 (1~, s), 5.54 (1~, t), 3.33 (2~, q), 2.18 (3~, s), 1.22 (3'~, d), 1.17 (3H, t), 0.~5 (3~, d).

This ~xample illustrates the herbicidal properties of compounds according to the inven~ion.
The herbicidal activity of the compounds was tested as follows:
Each chemical was formulated by dissolving it in an appropriate amount, dependent on the final spray volumef of a solvent/surfactant blend which comprised 78.2 gm/litre of Tween 20 and 21.8 gm/litre of Span 80 adjusted ~:

W 0 93/1~599 ~ 38 - PCT/~B93/00542 to 1 litre using methylcyclohexanone. ~ween 20 is a Trade Mark for a surface-active agent comprising a condensate of 20 molar proportions of ethylene oxide with sorbitan laurate. Span 80 is a Trade Mark for a surface-active agent comprising sorbitan mono-laurate. If the chemical did not dissolve, the volume was made up to 5cm3 with water, glass beads were added and this mixture was then shaken to effect dissolution or suspension of the chemical, after which the beads were removed. In all cases, the mixture was then diluted with water to the required spray volume. If sprayed independently, volumes o~ 25cm3 and 30cm3 were required for pre-emergence and post-emergence tests respectively; if sprayed together, 45cm was required. The sprayed aqueous emulsion contained 4X of the ~initial solvent/surfactant mix and the test chemical at an appropriate - concentration.
The spray compositions so prepared were sprayed onto young pot plants (post-emergence test) at a spray volume equivalent to 1000 li~res per hectare for Compound Numbers 1 to 22 and 400 litres per hectare for Com~pound Numbers 23 to 94.~ Damage to plants was assessed 13 days after ; spraying~by comparison with untreated plants, on a scale ~f O to 9 where Ois O~damage, 1 is 1-5Z damage, 2 is 6-15X damage, 3 is 16-25Z damage, 4 is 26~3SX damage, 5 is 36-59% damage, 6 is 60-69% damage, 7 is 70-79% damage, 8~is 80-89Z damage and 9 is 90-lOOZ damage.
The~designation n_~ indicaees that a compound wàs not tested against the~indicated species.
The~ rèsults of the tests are given in Table III below.

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Abbreviations used for Test Plants _ BV - Sugar beet BN - Rape GM - Soybean ZM - Maize OS - Rice TA - Winter wheat PA - Polygonum aviculare CA - Chenopodium album `GA - Galium ~
AR - Amaranthus retroflexus BP ~ ~
EH - llup rbi a he teropvl la AT - Abutilon ~heophrasti XT - Xanthium strumarium AF - Avena fatua ~-~M _ . Alopecurus osu~
GPY~n.~2~, "' SH - Sor~hum 5V - Setaria viridis DS - ~5 EC ~ Echinochloa ~E~
CE - ~ esculentus MI - Matricaria per~orata L~ - Lolium ~
PD - Paniucum di cotomi f i rum WO 93J19599 PCl`/GB93/00542 C~EMICAL FORMULAE
( IN DESCRIPTION ) f~ :
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Claims (21)

- 50 -

1. A herbicidal composition comprising a compound of the formula (I) or (IA) or (IB) in admixture with a herbicidally acceptable carrier or diluent:- (I) (IA) (IB) wherein Y represents (IC) or (ID) or (IE) and wherein R2 is a group CO-XR3 wherein X is O or S and R3 is hydrogen or an agrochemically acceptable ester-forming radical; or R2 is a group -R4 wherein R4 is an optionally substituted aryl or heterocyclic group; or R2 is a group CO-NR5R6 wherein R5 and R6 are the same or different and each represent an agrochemically acceptable amide-forming radical; stereoisomers of the compounds of formula (I), (IA) and (IB) and salts of the compound of formula (I), (IA) and (IB) wherein R2 is COXR3, X is O and R3 is hydrogen.

2. A composition as claimed in claim 1 wherein R2 is a group CO-XR3 and X
is oxygen.

3. A composition as claimed in claim 1 or claim 2 wherein R2 is a group CO-XR3 and R3 is optionally substituted C1 to C20 alkyl, optionally substituted C2 to C20 alkenyl, optionally substituted C2 to C20 alkynyl, optionally substituted C3 to C7 cycloalkyl, optionally substituted aryl or optionally substituted heterocyclyl.

4. A composition as claimed in claim 3 wherein the optional substituents which may be present in optionally substituted alkyl, alkenyl or alkynyl groups R3 are C3-7 cycloalkyl, C1-10 alkoxy C1-10 alkylthio, C2-8 alkenoxy, C2-8 alkenylthio, C2-8 alkyneoxy, C2-8 alkynylthio, halogen, halo-C1-10 alkoxy, halo-C2-8alkeneoxy, halo-C2-8alkynoxy, carboxy, C1-6 alkoxycarbonyl, carbamoyl, optionally substituted aryl, optionally substituted heterocyclyl, hydroxy, cyano, nitro, C1-6alkanoyloxy, amino, mono- and di-(C1-6)alkylamino;
and wherein the optional substituents which may be present in C3-7 cycloalkyl groups, R3 include C1-6alkyl, halo-C1-6alkyl, C1-10 alkoxy, C1-10 alkylthio, C2-8 alkenyl, C2-8 alkeneoxy, C2-8 alkenylthio, C2-8 alkynyl, C2-8 alkyneoxy, C2-8 alkynylthio, halogen, carboxy, C1-6 alkoxycarbonyl, carbamoyl, optionally substituted aryl, optionally substituted heterocyclyl, hydroxy, cyano, nitro, C1-6alkanoyloxy, amino, mono- and di-(C1-6)alkylamino;
and wherein the optional substituents which may be present in the aryl or heterocyclyl groups are independently selected from halogen, C1-6alkyl, C1-6alkoxy, C1-6alkylthio, halo(C1-6)alkyl, hydroxy(C1-6)alkyl, halo(C1-6)alkoxy, C2-8 alkenyl, C2-8 alkeneoxy, C2-8 alkenylthio, C2-8 alkynyl, C2-8 alkyneoxy, C2-8 alkynylthio, hydroxy, cyano, nitro, amino, mono- and di- C1-6 alkylamino, C1-6 alkanesulphinyl, C1-6 alkane sulphonyl, carboxy, C1-6alkoxycarbonyl, and C1-6alkoxycarbonyl(C1-6)alkyl groups.

5. A composition as claimed in claim 3 or claim 4 wherein R3 is a C1 to C10 alkyl group which may be unsubstituted or optionally substituted by hydroxy, halogen or cyano.

6. A composition as claimed in claim 3 or claim 4 wherein R is a C2 to C10 alkenyl group which may be unsubstituted or optionally substituted by hydroxy, halogen or cyano provided that the alkenyl group is not substituted by hydroxy when it is a vinyl group.

7. A composition as claimed in claim 1 wherein R2 is a group CO-XR3 and R3 is a C1-10 alkyl group substituted by a group -A-R11 wherein A is O
or a group S(O)x wherein x is 0, 1 or 2 and R is an optionally substituted C1 to C10 akyl group, an optionally substituted C2 to C8 alkenyl group, an optionally substitued C2 to C8 alkynyl group, an optionally substituted phenyl group, an optionally substituted C1-6 alkyl carbonyl group, an optionally substituted C3-7 cycloalkyl group or an optionally substitututed C3-7 heterocyclic group.

8. A composition as claimed in claim 7 wherein R3 is a C1-4 alkyl group substituted by a group -A-R11 wherein A is O or S and R11 is an optionally substituted C1 to C6 akyl group, an optionally substituted - 52a -C2 to C6 alkenyl group, an optionally substitued C2 to C6 alkynyl group, an optionally substituted phenyl group, an optionally substituted C1-6 alkyl carbonyl group, an optionally substituted C3-6 cycloalkyl group or an optionally substituted aliphatic C3-7 oxygen-containing heterocyclic group.

9. A composition as claimed in claim 1 wherein wherein R2 is a group CO-XR3 and R3 is the group -(CH2)n'-A-CH=CH-R wherein n' is an integer from 1 to 4 A is O or a group S(O)x where x is 0, 1 or 2 and R12 is hydrogen or a C1 to C4 alkyl group.

10. A composition as claimed in claim 1 wherein R2 is a heterocyclic group -R4 and R4 is a group of formula (II):
(II) wherein R14 and R15, which may be the same or different, are independently selected from hydrogen, optionally substituted phenyl, optionally substituted C1 to C20 alkyl, optionally substituted C2 to C8 alkenyl, optionally substituted C2 to C8 alkynyl, optionally substituted heterocyclyl or C3 to C7 cycloalkyl, X is a divalent group, -Y'-C=C- and Y' is oxygen or sulphur.

11. A composition as claimed in claim 10 wherein R4 is an optionally substituted oxazol-2-yl group.

12. A composition as claimed in claim 1 wherein R2 is a group CO-XR3 and R3 is a group -Z-CO-R8 wherein Z is a C1 to C12 alkylene group and R8 represents an optionally substituted C1-10 alkyl group, an optionally substituted C3-8 cycloalkyl group, an optionally substituted C2-10 alkenyl group, an optionally substituted C2-10 alkynyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted cycloalkylalkyl group or an optionally substituted heterocyclyl group.

13. A composition as claimed in claim 1 wherein R2 is a group CO-NR5R6 and wherein R5 and R6 are the same or different and may each independently be:
(a) hydrogen or (b) an optionally substituted C1-20 alkyl group, an optionally substituted C2-20 alkenyl group or an optionally substituted C2-20 alkynyl group or (c) optionally substituted C3 to C7 cycloalkyl or (d) optionally substituted aryl or (e) optionally substituted heterocyclyl; or (f) R5 and R6 together with the nitrogen atom to which they are attached represent an optionally substituted C5-7 heterocyclic ring or (g) R5 is hydrogen and R6 is a group -NR22-R23R24 wherein R22 is hydrogen or C1-6 alkyl are R23 and R24, which may be the same or different, may independently take any of the meanings given for R5 and R6 under (a), (b), (c), (d), (e) and (f) above or (h) R6 is a group -NR22-N=CR23R24 wherein R22, R23 and R24 have the meanings given previously or (i) R5 is hydrogen and R6 is a group -CR25R26-CO-W or - NR27-CO-W
wherein W is optionally substituted phenyl or optionally substituted heterocyclyl, R25, R26 and R27 are indendently hydrogen or optionally substitued C1-6 alkyl groups.

14. A composition according to claim 13 wherein R5 is hydrogen or a C1-4 alkyl group and R6 is a C1-4 alkyl group, each of which alkyl groups may independently be optionally substituted by C3-7 cycloalkyl, C1-4 alkoxy, halogen, carboxy, C1-6 alkoxycarbonyl, carbamyl, optionally substituted aryl, optionally substituted heterocyclyl, hydroxy, C1-6 alkanoyloxy, amino, mono- or di-(C1-6)alkylamino or wherein R5 and R6 together with the nitrogen atom to which they are attached represent an optionally substituted C5-6 aliphatic heterocyclic ring.

15. A composition acording to claim 14 wherein R5 and R6 together with the nitrogen atom to which they are attached represent morpholinyl, piperidyl, piperazinyl, or pyrolidinyl, each of which may be optionally substituted by halogen or C1-4 alkyl.

16. A compound of the formula (I) or (IA) or (IB) in claim 1 wherein R2 is a group CO-XR3X, is O or S and R3 is a C1-10 alkyl group substituted by a group -A-R11 wherein A is O or a group S(O)x wherein x is 0, 1 or 2 and R11 is an optionally substituted C1 to C10 alkyl group, an optionally substituted C2 to C8 alkenyl group, an optionally substituted C2 to C8 alkynyl group, an optionally substituted phenyl group, an optionally substituted C1-6 alkyl carbonyl group, an optionally substituted C3-7 cycloalkyl group or an optionally substitututed C3-7 heterocyclic group, provided that R3 is not a group -(CH2)2- when R11 is ethyl.

17. A compound as claimed in claim 16 wherein R3 is a C1-4 alkyl group substituted by a group -A-R wherein A is O or a group S(O)x wherein x is 0, 1 or 2 and R11 is an optionally substituted C1 to C6 akyl group, an optionally substituted C2 to C6 alkenyl group, an optionally substituted C2 to C6 alkynyl group, an optionally substituted phenyl group, an optionally substituted C1-6 alkyl carbonyl group, an optionally substituted C3-6 cycloalkyl group or an optionally substituted aliphatic C3-7 oxygen-containing heterocyclic group provided that R3 is not a group -(CH2)2- when R11 is ethyl.

18. A compound as claimed in claim 17 wherein wherein R3 is the group -(CH2)n'-A-CH=CH-R12 wherein n' is an integer from 1 to 4 A is O or a group S(O)x wherein x is 0, 1 or 2 and R12 is hydrogen or a C1 to C4 alkyl group.

19. A compound of formula (VI):

(VI) wherein R2 is selected from the group consisting of -CO-O-CH2-(3-bromophenyl) -CO-O-CH2-(3-methylphenyl) -CO-O-CH2-(4-hydroxymethylphenyl) -CO-O-(CH2)8-Br -CO-O(CH2)15CH3 -CO-O-(CH2)2-O-CH2-CH=CH2 -CO-O-(CH2)2-O-CH=CH2-CH3 -CO-O-(CH2)3-CH=CH2 -CO-O-(CH2)2-O-phenyl -CO-O-(CH2)2-O-(4-chlorophenyl) -CO-O-(CH2)2-O-CO-CH3 -CO-O-(CH2)2-O-CH2-CO-OC2H5 -CO-O-(CH2)3-C?CH
-CO-O-(CH2)4-O-CH=CH2 -CO-O-(CH2)3-O-CH=CH2 -CO-O-(CH2)2-O-CH=CH-(CH2)3-CH3 -CO-O-CH-(CH3)2 -CO-O-CH2-C(CH3)3 -CO-O-(cyclohexyl) -CO-O-(CH2)2-O-(CH2)2-O-CH3 -CO-O-(CH2)2-O-CH2-C?CH
-CO-O-(CH2)2-O-CH2-CH=CHCl -CO-O-CH(CH3)-CO-O-C2H5 -CO-O-CH2-CH=CHCl -CO-O-CH(CH3)-CH=CH2 -CO-O-CH2-CH=CHCH3 -CO-O-(4-chlorophenyl) -CO-O(3-nitrophenyl) -CO-O-(4-methoxyphenyl) -CO-O-CH2-(furan-2-yl) -CO-O-CH2-CH2Cl -CO-NH-(2,4-dichlorophenyl) -CO-NH-(2,5-dichlorophenyl) -CO-N(CH3)-(2,4-dichlorophenyl) -CO-O-(CH2)2-S-CH=CH2 -CO-S-(CH2)2-O-CH=CH2 -CO-O-CH2-O-CH=CH2 -CO-O-(CH2)9CH3 -CO-NH(CH2)2-OH
-CO-NH-(CH2)2-O-C2H5 -CO-N(-CH2-CH=CH2)2 -CO-NH-N(CH3)2 -CO-NH-N=C(CH3)2 -CO-N(CH2-CH2-OH)2 -CO-O- (CH3)3S+
-CO-O-CH2-cyclopropyl -CO-O-(CH2)2-O-CH2-CH=CH-CH2-CH2-CH3 -CO-O-(CH2)2-O-C H(C3H7)-CH=CH2 -CO-O-CH2-CH2-O-CH(CH3)-CH3 -CO-O-CH(CH3)-CH2-O-CH2-CH3 -CO-O-CH2-CH2-O-(cyclopropyl) -CO-O-CH2-CH(CH3)-O-CH2-CH3

20. A compound of formula (IB):
(IB) wherein R2 is selected from the group consisting of -CO-O-CH2-CH2-O-CH=CH2 -CO-O-(CH2)2-OH

21. A process of severely damaging or killing unwanted plants, which comprises applying to the plants or to the growth medium of the plants a heribicidally effective amount of a compound of the formula (I) or (IA) or (IB) in claim 1 wherein R2 is as defined in any of claims 1 to 15 or a herbicidally effective amount of a compound as claimed in any of claims 16 to 19.