CA2043704A1 - Compounds - Google Patents

Abstract

ABSTRACT

NOVEL COMPOUNDS

A compound of formula (I):

(I) where R1 is alkyl, optionally substituted aryl or optionally substituted heterocyclyl;
R2 is hydrogen, optionally substituted lower alkyl, lower alkoxy, cycloalkyl, haloalkyl, lower thioalkyl, halo or cyano; or the group R1 is a group of sun formula (i):

(i) where q is O or an integer of from 1 to 4 and groups R6 are selected independently from hydroxy, alkyl, alkoxy, alkylcarbonyl, halogen, nitrile, nitro, haloalkyl and haloalkoxy; X is oxygen or sulphur, p is 0 or 1, n is 0 or 1 and m is 1, 2 or 3 provided that when n is 0, p+ m is 2 or 3 and when n is 1, p+ m is 1 or 2;
R3 and R4 are independently selected from hydrogen, halo, alkyl or alkoxy or R3 and R4 together with the carbon atom to which they are attached form a carbocyclic ring; and R5 is CN; CO2R7 where R7 is hydrogen, a cation or an esterifying group; a group -CYNR8R9 where Y is oxygen or sulphur and R8 and R9 are independently selected from hydrogen, hydroxy, alkyl or alkoxy or together with the nitrogen atom to which they are attached form a heterocyclic ring; or R8 together with R3 and the group to which it is attached form a heterocyclic ring, or. R5 is a group of sub formula (ii) ABSTRACT (continued) (ii)

Description

~ PP 357~1 2V~ 3 ~
NOVEL COMPOUNDS

The present invention relates to oxime ether derivatives which are useful as herbicides, to process for their preparation and herbicidal compositions containing them.
According to the present invention there is provided a compound of formula (I):
where Rl is alkyl, optionally substituted aryl or optionally substituted heterocyclyl;
R is hydrogen, optionally substituted lower alkyl, lower alkoxy, cycloalkyl, haloalkyl, lower thioalkyl, halo or cyano; or the group is a group of sub formula (i): R2.
where q is O or an integer of from l to 4 and groups R6 are selected independently from hydroxy, alkyl, alkoxy, alkylcarbonyl, halogen, nitrile, nitro, haloalkyl and haloalkoxy; X is oxygen or sulphur, p is O or 1, n is 15 0 or l and m is 1, 2 or 3 provided that when n is 0, p+ m is 2 or 3 and when n is 1, p+ m is 1 or 2;
R3 and R4 are independently selected from hydrogen, halo, alkyl or alkoxy or R3 and R4 together with the carbon atom to which they are attached form a carbocyclic ring; and R5 is CN; Co2R7 where R7 is hydrogen, a cation or an esterifying group; a group -CYNR8R9 where Y is oxygen or sulphur and R8 and R9 are independently selected from hydrogen, hydroxy, alkyl or alkoxy or together with the nitrogen atom to which they are attached form a heeerocyclic ring;
or R8 together with R3 and the group -C(O)N- to which it is attached form a heterocyclic ring, or R5 is a group of sub formula (ii) where R10, R11, R12 and R13 are independently seleceed from hydrogen or alkyl; or a group S()r R14 where r is 0, 1 or 2 and R14 is hydroxy, lower alkyl or aryl.
In particular, the invention provides compounds of formula tI) where Rl is alkyl, optionally substituted aryl or heterocyclyl;
R is hydrogen, optionally substituted lower alkyl, lower alkoxy9 cycloalkyl, haloalkyl, lower thioalkyl, halo or cyano; or the group is a group of sub formula (i):

- 2 - 6 2 ~ ~d3 7 where q is 0 or an integet of from 1 to 4 and groups R are selecte independently from hydroxy, alkyl, alkoxy, alkylcarbonyl, halogen9 nitrile, nitro, haloalkyl and haloalkoxy; X is oxygen or sulphur, p is 0 or 1, n is 0 or 1 and m is 1, 2 or 3 provided that when n is 0, p+ m is 2 or 3 and when n is 1, p+ m is 1 or 2;
R3 and R4 are independently selected from hydrogen, halo, alkyl or alkoxy or R3 and R4 together with the carbon atom to which they are attached form a carbocyclic ring; and R5 is CN; C02R7 where R7 is hydrogen, a cation or an esterifying group; or a group CoNR8R9 where R8 and R9 are independently selected from hydrogen, alkyl or alkoxy or together with the nitrogen atom to which they are attached form a heterocyclic ring; or R8 together with R3 and the group -~N- to which it is attached form a heterocyclic ring, or R5 is a group of sub formula (ii):
where R10, R11, R12 and R13`are independently selected from hydrogen or alkyl; or a group S()r R14 where r is 0, 1 or 2 and R14 is hydroxy, lower alkyl or aryl.
As used herein the terms "alkyl" and "alkoxy" refer to straight or branched chain alkyl or alkoxy groups respectively, suitably having from 1 to 10 and preferably from 1 to 6 carbon atoms. The qualification "lower"
means that the number of carbon atoms present is suitably from 1 to 4.
Similarly the term "haloalkyl" refers to an alkyl group as defined above substituted by one or more halogen atoms. Suitable halogen atoms for haloalkyl and halo groups include fluorine, chlorine, bromine and iodine.
~5 The term "aryl" used herein includes phenyl and napthyl. The term "heterocyclyl" includes ring systems having 5 or 6 ring atoms, up to 3 of which are selected from oxygen, nitrogen and sulphur.
Suitably R1 is an optionally substituted aryl in pareicular phenyl or heterocyclic group.
Examples of substituents for aryl or heterocyclic groups Rl include one or more groups selected from hydroxy, alkyl, alkoxy, alkylcarbonyl, halogen, nitrile, amino, nitro, haloalkyl, haloalkoxy, or a group S(o)tR15 where t is 0, 1 or 2 and R15 is alkyl.
Suitable substituents for aryl groups R1 includes one or more groups selected from hydroxy, alkyl, alkoxy, alkylcarbonyl, halogen, nitrile, 2 ~

nitro, haloalkyl and haloalkoxy.
Preferred substituents for aryl groups R1 are C(1 6) alkyl, C(1 6) alkoxy, lower alkyl carbonyl, halo C~1 6) alkoxy or halo wherein the halo groups are selected from fluorine, chlorine, bromine and iodine.
Particular examples of the substituents are methyl, methoxy, ethoxy, bromo, fluoro or chloro.
Further examples include amino or S02CH3.
Preferably the substituents are in the ortho or meta position on the phenyl ring, most preferably on the ortho position.
Examples of heterocyclic groups Rl include pyridyl, thiophenyl, pyrrole, furyl and thiazolyl.
Suitable heterocyclic groups R1 include pyridyl, thiophenyl, pyrrole and furyl and thiazolyl.
Suitable substituents for heterocyclic groups R1 include alkyl in particlar methyl. The substituents may be attached to a carbon or heteroatom where possible. In particular the substituted may be attached to a nitrogen atom in the ring.
Suitable optional substituents for alkyl groups R include those listed above in relation to aryl or heterocyclic groups Rl.
Examples of groups R2 are hydrogen, lower alkyl, lower alkoxy, lower haloalkyl, C3_6 cycloalkyl, lower thio alkyl, halo or cyano.
In particular R is hydrogen, methyl, ethyl, tri~luoromethyl, iso-propyl, methoxy, cyclopropyl or thiomethyl.
Suitably R2 is hydrogen, lower alkyl, lower alkoxy, C3 6 cycloalkyl, lower thio alkyl, halo or cyano.
In particular R2 is hydrogen, methyl, ethyl, iso propyl, methoxy, cyclopropyl, thio methyl or cyano.
When R1 and R2 together form a cyclic group of sub formula (i) suitable groups are those where n is 0. Particular groups are those where 30 n is 0, p is 0 and m is 2 or 3 or n is 0, p is 1 and m is 2.
Preferably X is oxygen.
Suitable groups R6 include those substituents list above for R1.
Preferably R6 is halogen such as fluorine. Preferably q is 0 or 1, most preferably 0.
Suitable groups R3 and R4 include hydrogen, lower alkyl, lower alkoxy or halo.

2 ~ i~ 3 ~ ~3 L~
Examples of groups R3 and R4 include halogen, methyl, methoxy, ethyl, ethoxy, iso-propyl or fluoro.
Par~icular examples of R3 or R4 are hydrogen, methyl, ethyl, methoxy, ethoxy or fluorine.
Preferably R3 and R4 are other than hydrogen.
Where R3 and R4 together form a carbocyclic ring, the ring suitably contains from 3 to 7 carbon atoms.
Suitable groups R5 are -CYNR8R9 where Y is 0 or S and R8 and R9 are independently selected from hydrogen, lower alkyl such as methyl or ethyl or hydroxy.
Suitable groups R5 are -CONR8R9 where R8 and R9 are independently selected from lower alkyl such as methyl or ethyl.
When R8 and R9 together with the nitrogen atom to which they are attached form a heterocyclic ring, suitable rings include pyrrolidine, morpholine or azetidine rings.
When R8 together with R3 and the C(O)N group to which it is attached form a heterocyclic ring, it suitably contains from 5 to 7 ring atoms, preferably 5 carbon atoms.
Uhere R5 is C02R7, suitable esterifying groups R7 include alkyl, alkenyl, alkynyl or phenyl any of which may be optionally substituted.
Suitable optional substituents for R include one or more groups selected from halo such as fluoro, chloro, bromo or iodo; hydroxy; C1 6 alkoxy; nitro; cycloalkyl; heterocyclic optionally substituted by oxo;
nitrile; phenyl optionally substituted by nitro, halo such as chloro, alkoxy or carboxy or salts or C1 6 alkyl esters thereof; or alkylsilyl groups such as trimethylsilyl.
When R7 is a cation, it is suitably selected from agriculturally acceptable cations such as sodium, potassium, calcium, anomonium or substituted ammonium ions. +
Suitable substituted ammonium ions are NRaRbRCRd where Ra, Rb, Rc and Rd are independently selected from hydrogen or optionally substituted alkyl.
Preferably Y is oxygen.
Preferably R5 is a group CYN~3R9.
S it bly R10 R11 R12 and R13, in sub formula (i) are hydrogen.

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~ 5 --When R5 is a group S(o)rR14, R14 is suitably lower alkyl in particular methyl or ethyl.
Particular examples of compounds of formula (I) are se~ out in Tables 1 to 3 below.

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_ 24 -TABLE II 2 Q ~ ~ 7 o ~

R6 ~X)p(C~2)m 3 4 5 (GH2)n/

COMPOUND m p n X R3 R4 R5 R6 140 3 0 - H CH3 CON(CH3)2 H
141 2 0 ~ CH3 CH3 CON(CH3)2 H
142 2 0 0 - H CH3 CON~CH3)2 H
143 2 1 0 0 H CH3 CON(CH3)2 H
144 2 0 ~ CH3 CH3 C02CH3 _ ~ ' TABLE III
3 7 ~ ~
R. (CH2)S
>---N-O--C ~1 R2 R4 \ C/ R9 COMPOUND NO Rl R2 R4 R9 145 Cl CH3 H CH3 Compounds of formula (I) can be prepared by reacting a compound of formula (II) wherein R1 and R2 are as defined in relation to formula (I);
with a compound of formula (III) wherein R3, R4 and R5 are as defined in relation to formula (I) and Z is a leaving group in the presance of a base.
Suitable bases include strong bases such as alkali metal hydrides in particular sodium hydride. Other suitable bases are weaker bases such as alkali metal carbonates for example potassium carbonate.
The reaction is suitably effected in organic solvent such as dimethylformamide (DMF), dimethylsuphoxide, elevated temperatures for examples of from 20 to 120C are suitably employed in the process.
Suitable leaving groups Z include halogen in particular chlorine and bromine, mesylate and tosylate.
Compounds of formula ~II) can be prepared by reacting a compound of formula (IV);
wherein R1 and R2 are as defined in relation to formula (I) with hydroxylamine or a salt thereof in the presence of a base ~ ~ ~ 7p~ Lsium carbonate. The reaction is suitably effected in an organic solvent such as a lower alcohol in particular methanol at temperatures of from 20 to 60 C.
Compounds of formula tII) and (IV) are known compounds and can be prepared from known compounds by conventional methods.
Compounds of formula (I) where R5 is a group Co2R7 can be converted to compounds of formula (I) where R5 is CONR8R9 by (a) removing the group R7, (b) converting the resultant acid ~o the acid chloride and (c) reacting the acid chloride with an appropriate amine. Each of the steps (a) to (c) involve standard chemical manipulations and suitable conditions and reactions are well known in the art. Processes of this type are included in the examples given hereinafter. Alternatively compounds of formula ~I) where R5 is C02R7 can be converted to a group where R7 is a different esterifying group by reacting the acid obtained in step (a) above with an appropriate esterifying reagent such as an alcohol in the presence of an acid. Again suitable conditions are exemplified hereinafter.
Uhen R5 is a group CSNR8R9 it may be prepared by thiolation of the corresponding compound where R5 is CoNR8R9 as exemplified hereinafter.
Compound of formula (I) where R8 is S(o)rR14 and r is 1 or 2 can be prepared by oxidation of corresponding compounds where r is 0. Oxidation is suitably effected by means of conventional oxidising agent such as potassium permanganate in a medium of glacial acetic acid under standard conditions.
Compounds of formula (I) wherein R5 is CO3R7 can be converted directly to compounds of formula (I) where R is CONR R by reac~ion with a compound of formula (V) wherein R8 and R9 are as defined in relation to formula ~I) and R16 and R17 are independently alkyl groups, for example methyl. The reaction is suitably carried out in an inert organic solvent such as dichloromethane at temperatures of from 25 to 50C. Suitably the reaction is effected under an inert atmosphere for example of nitrogen.
Compounds of formula (V) can be prepared ln situ by reacting a compound of formula (VI) wherein R16, R17 and R18 are independently alkyl groups with an amine of formula (VII) - 27 - 2 ~ l~ 3 ~ ~ ~
wherein R8 and R9 are as defined in relation to formula (I) at low temperatures for example of from 0 to 10C
A suitable compound of formula (VI) is trimethylaluminium.
This type of reaction is illustrated in Tet. Letts. 4171, 1977, S
Weinreb, Colorado State University. In some cases, the compound of formula (I) where R5 is C02R7 can be converted to compounds where R5 is CoNR3R9 by reaction directly with a compound of formula VII. This reaction is particularly useful when R8 and R9 together with the nitrogen atoms to which they are attached form a heterocyclic ring. The reaction is suitably carried out in an inert organic solvent such as methanol at moderate temperature of from 20 to 60C, conveniently at ambient temperature.
The compounds of the invention are capable of controlling the growth of a wide variety of plants and in aprticular some show a useful selectivity in crops such as soya, mai~e, rice and winter wheat. They may be applied to the soil before the emergence of plants (pre-emergence application) or they may be applied to the above ground parts of growing plants (post-emergence application). In general the compounds are more active by pre emergence application. In another aspecy~ therefore, the invention provides a process of inhibiting the growth of unwanted plants, ~ by applying to the plants, or to the locus thereof, a compound of the formula (I) as hereinbe~ore defined. The rate of application required to inhibit the growth of unwanted plants will depend on, for example, the particular compound of formula (I) chosen for use, and the particular species of plant it is desired to control. However, as a general guide, an ~5 amount of from 0.01 to 5.0 kilograms per hactare, and preperably 0.025 to 2 kilograms per hectare is usually suitable.
The compounds of the invention are preferably applied in the form of a composition, in which the active ingredient is mixed with a carrier comprising a solid or liquid diluent. In another aspect, therefore, the invention provides a herbicidal composition, comprising as an active ingredient a compound of the formula (I) as hereinbefore defined, in admixture with a solid or liquid diluent. Preferably the composition also comprises a surface active agent.
The solid compositions of the invention may be for example, in the form of dusting powders, or may take the form of granules. Suitable solid diluents include, for example, kaolin, bentonite, kieselguhr, dolomite, 2~-~37~

calcium carbonate, talc, powdered magnesia and Fuller's earth. Solid compositions also include soluble powders and granules which may comprise a compound of the invention in admixture with a water soluble carrier.
Solid compositions may also be in the form of dispersible powders or grains comprising in addition to the active ingredient, a wetting agent to facilitate the dispersion of the powder or grains in liquids. Such powders or grains may include fillers, suspending agents and the like.
Liquid compositions include solutions, dispersions and emulsions containing the active ingredient preferably in the presence of one or more surface active agents. Water or organic liquids may be used to prepare solutions, dispersions, or emulsions of the active ingredient. The liquid compositions of the invention may also contain one or more corrosion inhibitors for example lauryl isoquinolinium bromide.
Surface active agents may be of the cationic, anionic or non-ionic type. Suitable agents of the cationic type include for example quaternary ammonium compounds, for example cetyltrimethylammonium bromide. Suitable agents of the anionic type include for example soaps, salts of aliphatic mono-esters of sulphuric acid, for example sodium lauryl sulphate; and salts of sulphonated aromatic compounds, for example dodecylbenzenesulphonate, sodium, calcium and ammonium lignosulphonate, butylnaphthalene sulphonate, and a mixture of the sodium salts of diisopropyl- and triisopropyl-naphthalenesulphonic acid. Suitable agents of the non-ionic type include, for example, the condensa~ion products of ethylene oxide with fatty alcohols such as oleyl alcohol and cetyl alcohol, or with alkyl phenols such as octyl=phenol, nonylphenol, and octylcresol.
Other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, for example sorbitol monolaurate; the condensation products of the said partial esters with ethylene oxide and the lecithins; and silicone surface active agents (water soluble surface active agents having a skeleton which comprises a siloxane chaib e.g.
Silwet L77). A suitable mixture in mineral oil is Atplus 411F.
The compositions which are to be used in the form of aqueous solutions, dispersions or eulsions are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, the concentrate being diluted with water before use. These concentrates are usally required to withstand storage for prolonged periods and after such ~ 29 ~
storage to be capable of dilution with water in order to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment.
The compositions of the invention may contain, in addition to carriers and surface active agents, various other constituents to increase their usefulness. They may contain, for example, buffering salts to maintain the pH of the compositions within a desired range; antiireeze agents, for example oils and humectants; and sequrstrants, for example citric acid and ethylenediaminetetracetic acid, which help to prevent the formation of insoluble precipitates when the compositions are diluted with hard water.
Aqueous dispersions may contain anti-settling agents and anti-caking agents. The compositions may in general contain a dye or pigment to impart a characyeristic colour. Agents for increasing viscosity may be added to reduce the formation of fine droplets during spraying, and thereby reduce spray drift. Other additives useful for particular pruposes will be known to those skilled in the formulation art.
In general concentrates may conveniently contain from 10 - 85% and preferably from 25 to 60% by weight of active ingredient. Dilute preparations ready for use may contain varying amounts of the active ingredient, depending upon the purpose for which they are to be used;
however, dilute preparations suitable for many uses contain between 0.01%
and 10% and preferably between 0.1% and 1% by weight of the active ingredient.
The compositions of the invention may comprise, in addition to one or more compounds of the invention, 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 comprising a mixture of at least one herbicidal compound of formula (I) as hereinbefore defined with at least one other herbicide.
The other herbicide may be any herbicide not having the formula (I).
It will generally be a herbicide having a complementary action in the particular application.
Examples of useful complementary herbicides include:

A. benzo-2,1,3-thiadiazin-~-one-2,2-dioxides such as bentazone;

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B. hormone herbicides, particularly the phenoxy alkanoic acids such as MCPA, MCPA-thioethyl, dichlorprop, 2,4,5-T, MCPB, 2 9 4-D, 2,4-DB, mecoprop, trichlopyr, clopyralid, and their derivatives (eg. salts, esters and amides);

C. 1,3 dime~hylpyrazole 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;

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2~37~
F. arylurea herbicides such as diuron, flumeturon, metoxuron, neburon, isoproturon, chlorotoluron, chloroxuron, linuron, monolinuron, chlorobromuron, daimuron, -5 methabenzthiazuron;

G. phenylcarbamoyloxyphenylcarbamates such as phenmedipham and desmedipham;

H. 2-phenylpyridazin-3-ones such as chloridazon and norflurazon;

I. uracil herbicides such as lenacil, bromacil and terbacil;

J. triazine herbicides such as atrazine, simazine~
aziprotryne, cyanazine, prometryn, dimethametryn, simetryne, and terbutryn;

K. phosphorothioate herbicides such as piperophos, bensulide, and butamifos;

L. thiolcarbamate herbicides such as cycloate, vernolate, molinate, thiobencarb, butylate , EPTC , tri-allate, di-allate, esprocarb, tiocarbazil, pyridate, and dimepiperate;

M. 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;

' ~ '': ' . , ;' . :~

2~3~a 0. anilide herbicides such as pretilachlor, butachlor, alachlor, propachlor, propanil, metazachlor, metolachlor, acetochlor, and dimethachlor;

P. dihalobenzonitrile herbicides such as dichlobenil, bromoxynil and ioxynil;

Q. haloalkanoic herbicides such as dalapon, TCA and salts thereof;

R. diphenylether herbicides such as lactofen, 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, quiæalofop and esters thereof and fenoxaprop and eseers thereof such as the ethyl ester;

T. cyclohexanedione herbicides such as alloxydim and salts thereof, sethoxydim, cycloxyidim, tralkoxydim, and clethodim;

, : ' `~. ' ; .
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, :- .
' , . :, U. sulfonyl urea herbicides such as chlorosulfuron, sulfometuron, metsulfuron and esters thereof; benzsulfuron and es~ers 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-methylureidosulphonyl) benzoic acid esters such as the methyl es~er thereof (DPX-LS300) and pyrazosulfuron;

V. imidazolidinone herbicides such as imazaquin, imazamethabenz, imazapyr and isopropylammonium salts thereof, imazethapyr;

W. arylanilide herbicides such as flamprop and esters thereof, benzoylprop-ethyl, diflufenican;
X. - amino acid herbicides such as glyphosate and glufosinate and their salts and esters, sulphosate and bialaphos;

Y. organoarsenical herbicides such as monosodium methanearsonate (MSMA);

Z. herbicidal amide derivative such as napropamide, propyzamide, carbetamide, tebutam, bromobutide, isoxaben, naproanilide and naptalam;

AA. miscellaneous herbicides including ethofumesate, cinmethylin, difen~oquat and salts thereof such as the methyl sulphate salt, clomazone, oxadiazon, bromofenoxim, barban, tridiphane, flurochloridone, quinchlorac and mefanacet;

BB. Examples of useful contact herbicides include:

bipyridylium herbicides such as those in which the active entity is paraquat and those in which the active entity is diquat;

* These compounds are preferably employed in combination with a safener such as dichlormid.

The complementary herbicide is suitably present in the mixture or composition in an amount such that it is applied at its conventional rate.
The following Examples illustrate the invention.

Preparation of N,N-Dimethyl-2-chloroacetophenon-eoxime-o-iso-butyramide (Compound No 6 in Table I) A solution of 2-chloroacetophenoneoxime (1.695g, lOmmol) in dimethylformamide (DMF) (dry, 4ml) was added dropwise to NaH(50% oil dispersion) (1.1 equiv; 0.264g, l~mmol) suspended in DMF (dry, 15ML) under N2, and the resulting mixture stirred at room temperature for 1 hour.
N,N-Dimethyl-a -bromoisobutyramide (1.94g, lOmmol) in dry DMF (3ml) was added dropwise to the mixture and the mixture heated at 100C for 36 hours.
~5 Another equivalent of N,N-dimethyl -a- bromoisobutyramide (1.94g, lOmmol) in dry DMF (3ml) was added and the resulting mixture heated for a further 20 hours. The reaction mixture was cooled, poured into H20 and extracted with EtOAc. The combined organic extracts were washed with brine, dried (MgS04), filtered and concentrated under reduced pressure to yield an oil residue. The product was purified by flash chromatography (eluted with 50%

:
~ - .
,; , hexane~Et20) to afford a white crystalline compound (0.39g, 14~) H NMR ~CDCl3): 1.6 [6H, s, C(CH3)2]; 2-25 (3H, s, 2 ~ ~ 3 7 Ol~
CH3-C=N); 2.~ 13H, bs, N(CH3)2], 3-1 13H, bs, N(CH3)2], and 7.3 (4H, m, aromatic C-H)-m.s. M+ 283 Preparation of Methyl-2-chloroace_oph-n-n-eoxime isobutyrate(Compound 32 in Table 1).

2-chloroacetophenoneoxime (4.24g, 25mmol) in DMSO (dry 5ml) was added dropwise to NaH (50~ oil dispersion) (1.2 equiv; 0.72g, 30mmol) suspended in DMSO (dry, 15ml) and the resulting mixture stirred at room temperature for 1 hour. Methyl-a-bromoisobutyrate (4.525g, 25mmol) in DMSO (dry, 5ml) was added dropwise to this green solution and the reaction mixture heated at 90C for 4 hours, then 110C for a further 8 hours. The mixture was cooled diluted with ice water and extracted with Et20. The combined organic extracts were washed with brine, dried (MgS04), filtered and the filtrate concentrated under reduced pressure to yield the product (4.73g, 70~).

1H NMR (CDCl3): 1.6 l6H, s, C(CH3)2]; 2-25 (3H, s, CH3-C=N); 3.70 (3H, s, C02CH3); and 7-3 (4H, m, aromatic C-H).

Step a Preparation of 2-chloroacetophenoneoxime-0-isobutyric acid.

Aqueous NaOH (1.2 equiv; 0.48g, 12mmol dissolved in 5ml of H20) was added dropwise to methyl-2-chloroacetophenoneoxime-0-isobutyrate (2.695g, lOmmol) dissolved in isopropanol (IPA) (25ml) and the resulting solution .
..

heated under reflux for 6 hours. The reaction mixture was cooled, IPA
removed under reduced pressure, to leave a semi solid residue. H ~ ~ s~ 7 added and the mixture acidified (2N HCl), and extracted with Et20. The combined organic extracts were washed with brine, dried tMgS04), filtered and the filtrate concentrated under reduced pressure to yield the product (2.38g, 93%).

lH NMR (CDCl3): 1.6 16H, s, C(CH3)2]; 2-3 (3H~ s, CH3C=N); and 7.3 (4H, m, aromatic C-H).

Step b Preparation of N?N-Dimethyl-2-chloroacetophenoneoxime-0-isobutyramide (Compound No. 6 in Table 1) A mixture of 2-chloroacetophenone-0-isobutyric acid (lg, 3.9mmol) and thionylchloride (5ml) was heated at 70C for 2 hours, and the reaction mixture was concentrated under reduced pressure. The resulting 2-chloroacetophenoneoxime-0-isobutylchloride was dissolved in a mixture of toluene (5ml) and Et3N (4 drops) and the solution cooled to 0C (ice bath).
Dimethylamine (2 eq., 0.35g, 7.8mmol) in toluene (2ml) was added dropwise and the mixture stirred at room temperature overnight. The reaction mixture was concentrated under reduced pressure, the residue diluted with water and extracted with EtOAC. The combined organic extracts were washed with brine, dried (MgS04), filtered and the filtrate concentrated under reduced pressure. The product was purified by preparative TLC (eluted with 50% hexane/Et20) to afford an oil which crystallised on standing (0.~5gp 77%).

lH NMR ( CDC13 ): See Example 1 E~AMPLE 4 Preparation of Azetidine-2-chloroacetophenoneoxime-0-isobutyramide (Compound No. 27 in Table 1).

. : . ~ . : .
;.
: .
.
.;
' !

- 37 - 2~37~l~
Trimethylaluminium (2M solution in hexane, 0.27g, 2ml, 3.8mmol) was added dropwise to azetidine (0.23g, 0.3ml, 45mmol) dissolved in CH2Cl2 (dry, 4ml) at -5C (ice salt ba~h) under N2, and the resulting mixture stirred at room temperature for 30 minutes.
Methyl-2-chloroacetophenoneoxime-0-isobutyrate (lg, 3.7mmol) in CH2Cl2 (dry, 3ml) was added dropwise and the reaction mixture heated under reflux for 6 hours. The reaction mixture was cooled, concentrated under reduced pressure to yield an oily residue. A mixture of Et20/EtOAc was added and the solid filtered off, the filtrate was concentrated under reduced pressure, dissolved in warm EtOH, and the insoluble solids again filtered off. The filtrate was concentrated under reduced pressure and the resulting oil triturated with pentane to yield the corresponding product (0.469g, 43~) 1H NMR (CDCl3): 1.5 [6H, s, C(CH3)2]; 2-2 15H, m~
CH3C=N and NCH2CH2CH2]; 4 0 l2H, t, NCH2CH2CH2]; 4-3 [2H, t, NCH2CH2CH2l;
and 7.3 (4H, m, aromatic C-H) ms 294 M+.

Preparation of 2-chloroacetophenoneoxime-0-isobutyronitrile. (Compound No.
28 in Table 1).

1. A mixture of 2-chloroacetophenoneoxime (1.61g, lOmmol),a-bromoisobutyronitrile (1.48g, lOmmol), K2C03 (anhydrous, 1.4eq, 2.07g, 15mmol), amd DMSO (dry, 15ml) were heated at 120C for a period of 28 hours. The reaction mixture was cooled, diluted with H20 and extracted with Et20. The combined Et20 extracts were washed with brine, dried (MgS04), filtered, and the filtrate concentrated under reduced pressure, to give an oily residue. The product was purified by flash chromatography (eluted with 50% Et20/hexane) in 14% yield.

- 38 - 2~37~
1H NMR (CDC13): 1.75 16H, s, C(CH3)2], 2-25 (3H, s, CH3C=N; and 7.35 (4H, m, aromatic C-H).

ms 236 M+

2. A mixture of 2-chloroacetophenaneoxime (1.61g, lOmmol), a-bromoisobutyronitrile (1.48g, lOmmol), sodium hydride 10.28g, 12mmol) a catalytic amount of potassium iodide and DMSO (dry, 14ml) were heated at 110C for a period of 8 hours. The reaction mixture was cooled, diluted with H~O and extracted with Et20. The combined E~20 extracts were washed with brine, dried (MgS04) filtered, and the filtrate concentrated under reduced pressure, to give an oily residue. After purification by flash chromatography (eluted wi~h 50% Et20/hexane) the product was obtained (0.41g)-Preparation of Ethyl-2-chloroacetophenoneoxime-0-isobutyrate. (Compound No. 29 in Table 1).
-A mixture of 2-chloroacetophenaneoxime-0-isobutyric_acid (0.3g, 12mmol), EtOH (dry, lOml?, and a catalytic amoun~ of p-toluenesulphonic acid were heated under reflux for 2 hours. The reaction mixture was cooled, concentrated under reduced pressure, and the residue dissolved in Et20. The Et20 layer was washed with water, dried (MgS04), filtered and the filtrate concentrated under reduced pressure. The product was purified by preparative TLC (eluted with 50% pentane Et20) to afford an oil.

1H NMR (CDCl3): 1.25 (3H, t, OCH2CH3) 1.55 [6H, s, C(CH3)2]; 2-25 (3H, s, CH3- C=N); 4.20 (2H, q, OCH2CH3), and 7.30 (4H, m, aromatic C-H~.

Preparation of Iso-propyl-2-chloroacetophenoneoxime-0-isobutyrate.
(Compound No. 30 in Table 1).

... ..

. . . : : ................................................. .
'~ :

This compound was prepared as described in Example 6 exce~t~ ~ ~ 7 isopropyl alcohol was employed in place of ethanol.

H NMR (CDCl3): 1.25 [6H, d, CH(CH)3~2], 1-55 (6~, s, C(CH3~2], 2-25 (3H, s, CH3C=N~, 5.0 (lH, s, CH(CH3~2], and 7.30 (4H, m, aromatic C-H~.

EXAMPL~ 8 The following compounds were prepared by methods analogous to those described in Example 1, except that the appropriate a-chloroaceto, propiono or isobutyramide derivatives was employed in place of the N,N-dimethyl-a-bromoisobutyramide:

N,N-Dimethyl-2-fluoroacetophenone-oxime-0-propionamide (Compound No. 13 in Table 1) (oil) structure confirmed by n.m.r.

N,N-Dimethyl-2-fluoroacetophenone-oxime-0-acetamide ~Compound No. 12 in Table 1); oil - structure confirmed by n.m.r.

N~N-Dimethyl-2-chloroacetophenone-o-acetamide (Compound No. 20 in Table 1);
pale yellow oil; structure confirmed by n.m.r.

N,N-Dimethylacetophenoneoxime-0-acetamide (Compound No. 1 in Table 1); m.p.
65-66C.

N,N-Dimethyl-2-chloroacetophenoneoxime-0-propionamide (Compound No. 24 in Table 1); oil, structure confirmed by n.m.r.

N,N-Dimethyl-isobutyrophenoneoxime-0-propionamide (Compound No. 19 in Table 1); oil structure confirmed by n.m.r.

N,N-Dimethyl-a-indaneoneoxime-0-propionomide (Compound No. 142 in Table 2);
m.p. 96-97C.

`. ~` ~ `

, ~ 40 - 2 ~ 1~ 3 7 ~ l~
N,N-Dimethyl-a-Tetraleneoneoxime-0-propionamide (Compound No. 140 in Table 2).

N,N-Dimethyl-2-Acetylthiopheneoxime-0-propionamide ~Compound No. 31 in Table 1); pale yellow oil - structure confirmed by n.m.r.

N,N-Dimethyl-2-methylacetophenoneoxime-0-isobutyamide (Compound No. 11 in Table 1); m.p. 33-88C.

N,N-Dimethyl-2-methylacetophenoneoxime-0-propionamide (Compound No. 10 in Table 1); oil; structure confirmed by n.m.r.

N,N-dimethyl-propiophenoneoxime-0-propionamide (Compound No. 9 in Table 1) oil, structure confirmed by n.m.r.

N,N-Dimethyl-2-ethoxyacetophenoneoxime-0-propionamide (Compound No. 7 in Table l) pale yellov oil, structure confirmed by n.m.r.

N,N-Dimethyl-2-chloroacetophenoneoxime-0-propionamide (Compound No. 25 in Table 1) oil, structure confirmed by n.m.r.

N,N-Diethylacetophenoneoxime-0-propionamide (Compound No. 4 in Table 1)pale yellow oil; structure confirmed by n.m.r.

N,N-Dimethyl-2-methoxyacetophenoneoxime-0-propionamide (Compound No. 5 in Table 1) oil; structure confirmed by n.m.r.

N,N-Dimethyl-4-Chloropropiophenoneoxime-0-propionamide (Compound No. 53 in Table l) m.p. 70-71C.

N,N-Dimethyl-l-acetonaphthoneoxime-0-propionamide (Compound No. 41 in Table 1) pale yellow viscous oil, structure confirmed by n.m.r.

Compound No. 33 in Table 1;
oil, structure confirmed by n.m.r.

:. .
,.
' ` `' ": ' -~1- 2a~3~
Compound No. 44 in Table 1; pale orange oil, structure confirmed by i.r.

The following compounds were prepared using methods analogous to those described in Example 1:

N,N-Dimethyl-2-fluoroacetophenoneoxime-0-isobutyramide (Compound No. 12 in Table 1) oil structure confirmed by n.m.r.

N,N-Dimethyl-2-fluorobenzaldoxime-0-isobutyramide (Compound No. 17 in Table 1) oil - structure confirmed by n.m.r.

N,N-Dimethylacetophenoneoxime-0-isobutyramide (Compound No. 2 in Table 1 oil structure confirmed by n.m.r.

N,N-Dimethylpropiophenononeoxime-0-isobutyramide (Compound No. 8 in Table 1) m.p. 49-50C.

Compound No. 18 in Table 1; oil, structure con~irmed by n.m.r.

Compound No. 21 in Table 1; oil, structure confirmed by n.m.r.

Compound No. 16 in Table 1;
m.pt 108 - 110C

Compound No. 23 in Table 1; oil, structure confirmed by n.m.r.

methyl-2-fluoroaceteophenoneoxime-0-methoxyacetate ~Compound No. 43 in Table 1).

This example illustrates the preparation of N-pyrrolidine-2-fluoroacetophenone oxime-0- methoxyacetamide (Compound No.
36 in Table 1).

~' ~

- 42 - 2 ~ ~ 3 ~
Compound 43 (1.4g~ prepared by methods analogous to those described in Example 1 was dissolved in methanol (20ml) and pyrrolidine (1.17g) added.
The reaction mixture was allowed to stand at ambient temperature for 18 hours after which the methanol was removed under reduced pressure. The residue was dissolved in hexane, washed with dilute hydrochloric acid, dried using magnesium sulphate and the solvent evaporated under reduced pressure. The product was purified by column chromatography on a silicon column eluted with dichloromethane. The product was then extracted into ethyl acetate which was then removed under reduced pressure to yield the desired product as a colourless oil (yield 0.83g). The structure was confirmed by n.m.r.

The following compounds were prepared by methods analo~ues to those described in Example 10:
N-morpholine-2-fluoroacetophenoneoxime-0-methoxy acetoamide (Compound No.
37 in Table 1) oil structure confirmed by n.m.r.
N,N-Dimethyl-2-fluoroacetophenoneoxime-0-methoxyacetolamide (Compound No.
35 in Table I) yellow oil, structure confirmed by n.m.r.

Compound No. 42 in Table 1; oil, structure confirmed by n.m.r.

This example illustrates the preparation of Compound No. 34 in Table 1 Step a Hydroxylamine hydrochloride (7.0g), cyclopropyl benzaldehyde t7.0g~, dry pyridine (lOml) and ethanol (50ml) was heated together under reflux for 2 hours. The solvent was removed under reduced pressure and water added.
The resultant solid was filtered off, dried under suction and recrystallised from carbon tetrachloride/60-80 petroleum ether.

. ' :
.

_ 43 - ~ ~ ~ 3~

Step b The product from step (a) (1.89g) was dissolved in dry acetonitrile t30ml) and N,N-dimethyl-~-bromoisobutyramide (2.0g) added together with a catalytic amount of potassium iodide. The mixture was heated under reflux with stirring for 16 hours, then cooled, water added and the mixture extracted into diethyl ether. The ether layer was washed with 5% sodium hydroxide solution (3xl5ml), dried over magnesium sulphate and evaporated under reduced pressure. The product was obtained as an oil whlch crystallised on standing.
After recrystallisation from hexane the desired product was obtained as a white powder (0.43g) m.p. 53-54C
Structure confirmed by n.m.r.

This example illustrates the preparation of Compound 46 in Table 1.

Step (a) Preparation of (1-chloroethyl)ethylsulphide.
To a stirred solution of diethylsulphide (31.7g) in carbon tetrachloride (lOOml) was added chlorine gas (25.0g) in carbon tetrachloride (300ml) dropwise over a period of 45 minutes. A temperature of -20C was maintained throughout the addition. After the addition was complete, the reaction was allowed to come to room temperature and then maintained at room temperature for 2 hours during which time hydrogen chloride gas evolved. The solvent was then removed under reduced pressure during which time the temperature was not allowed to exceed 30C. The resultant colourless oil was removed and distilled at a 40mm (51C).

Step (b) Acetophenoneoxime (lg), the product from step (a) (0.92g), sodium hydride (0,18g) and dry dimethylsulphoxide (5ml) were stirred together at room temperature for 2 hours. The reaction mixture was then poured into water ' ~

2~'~37~

and extracted into hexane. The hexane layer was washed with 5% sodium hydroxide solution, dried over magnesium sulphate and evaporated under reduced pressure to yield a pale yellow oil. This was distilled on a high vacum pump to give the desired product as a colourless oil (0.5g) which distiiled at 87C/O.lnm. The structure was confined by n.m.r.

The following compounds were prepared by methods andogous to that described in Example 13.
Compound 55 in Table 1; structure confined by n.m.r.

Preparation of Compound No. 60 in Table I.
Compound 55 (2.0g) in glacial acetic acid (20ml) cooled in a water bath and potassium permanganate (1.84g) in water (50ml) dripped in over a period of 15 minutes. The reaction mixture was stirred at room temperature for 2 hours after which sulphur dioxide gas was passed through the solution. Water (25ml) was added and the reaction mixture extracted into trichloromethane (50ml) dried over magnesium sulphate and the solvent removed under reduced pressure to give the desired product as a colourless oil. (Structure confined by n.m.r.).

The following compounds were prepared by methods analogous to these described in Example lS:

Compound 47 in Table l; m.pt. 63-65C

Compound 45 in Table l; m.pt. 50-51C
~5 EXAMPLE 17 The following compounds were prepared by a method analogous to that described in Example 4 except that dimethylamine was used instead of azelidine:

-;
,~
, : .

2~ ~37 ~i~
N,N-Dimethyl-2-aminoacetophenone oxime-0-isobutyramide (Compound No. 69 in Table 1~ - Pale brown solid - structure confined by n.m.r.
N,N-Dimethyl-trifluoroacetophenone-0-isobutyramide (Compound No. 70 in Table 1) oil - structure confirmed by n.m.r.
N,N-Dimethyl-2-nitroacetophenone oxime-0-isobutyramide (Compound No. 71 in Table 1) - oil - structure confirmed by nmr.
N,N-Dimethyl-2-chloro,6-trifluoroacetophenone oxime-0-isobutyramide (Compound No. 75 in Table 1) oil - structure confirmed by n.m.r.
Compound No. 77 in Table 1 - oil structure confirmed by n.m.r.
N,N-Dimethyl-2,6-dichloroacetophenone oxime-0-isobutyramide ~Coimpound No.
81 in Table 1) - oil structure confirmed by n.m.r.
N,N-Dimethyl-2-methylsulphonacetophenone oxime-0-isobutyramide (Compound No. 82 in Table 1) - off white solid - structure confirmed by n.m.r.
N,N-Dimethyl-2,6-difluoroacetophenone oxime-0-isobutyramide (Compound No.
83 in Table 1) - oil structure confirmed by n.m.r.
N,N-Dimethyl-2,5-dichloroacetophenone oxime-0-isobutyramide (Compound No.
84 in Table 1) - oil structure confirmed by n.m.r.
N,N-Dimethyl-2,3-dichloroacetophenone oxime--0-isobutyramide (Compound No.
85 in Table 1) - oil, semi-solid on standing - structure confirmed ny n.m.r.
N,N-Dimethyl-3,5-bis-trifluoromethylacetophenone-oxime-0-isobutramide (Compound No. 86 in Table 1) oil - structure confirmed by n.m.r.
Compound No. 87 in Table 1 - oil-structure confirmed by n.m.r.
N,N-Dimethyl-2,3-di~luoroacetophenGne oxime-0-isobutyramide (Compound No.
88 in Table 1) - oil, semi-solidified on standing - structure confirmed by n.m.r. and m.s.

The following compounds were prepared substantially as described in Example 4 except that dimethylamine was used instead of azetidine and slightly different reaction conditions were used. In particular the reaction mixture was stirred at room temperature ins~ead of under reflux and work-up was effected by dilution with water, extraction into ethyl acetate and dried over magnesium sulphate.
Compound No. 109 in Table 1 - orange oil structure confirmed by n.m.r.
Compound No. 110 in Table 1 - pale yellow oil structure confirmed by n.m.r.
Compound No. 111 in Table 1 - orange oil structure confirmed n.m.r.

- 46 ~ 3 7 ~
Com2ound No. 112 in Table 1 - pale yellow oil structure confirmed by n.m.r.
Compound No. 113 in Table 1 - pale yellow oil structure confirmed by n.m.r.
Compound No. 114 in Table 1 - orange oil - structure confirmed by n.m.r.
Compound No. 115 in Table 1 - orange oil structure confirmed by n.m.r.
Compound No. 116 in Table 1 - orange oil structure confirmed by n.m.r.
Compound No. 117 in Table 1 - orange oil structure confirmed by n.m.r.
Compound No. 118 in Table 1 - dark orange oil structure confirmed by n.m.r.
Compound No. 119 in Table 1 - oil structure confirmed by n.m.r.
Compound No. 130 in Table 1 - orange oil structure confirmed by n.m.r.
Compound No. 131 in Table 1 - oil structure confirmed by n.m.r.
Compound No. 133 in Table 1 - oil structure confirmed by n.m.r.

The following examples were prepared using the method of Example 3 step (b) except that where necessary dimethylamine was replaced by the appropriate alkylamine:
N-isopropyl-2-chloroacetophenoneoxime-0-isobutyramide (Compound No. 72 in Table 1) - oil - structure confirmed by n.m.r.
N-t-butyl-2-chloroacetophenone oxime-O-isobutyramide (Compound No. 73 in Table 1 - oil stricture confirmed by n.m.r.
Compound No. 74 in Table 1 - oil structure confirmed by n.m.r.
Compound No. 76 in Table 1, - oil structure confirmed by n.m.r.
N-Ethyl-N-methyl-2-chloroacetophenone oxime-O-isobutyramide (Compound No.
78 in Table 1) - oil structure confirmed by n.m.r.

This example illustrates the preparation of Compound No. 80 in Table 1.
To a stirred mixture of hydroxylamine hydrochloride (2 equiv, 0.695g, lOmmol) in dry methanol (lOcm3) was added potassium hydroxide (3 equiv) (0.84g, 15mmol in methanol (3cm3)). This mixture was stirred for ~ hour at room temperature, then a solution of methyl-2-chloroacetophenone oxime-O-isobutyrate (1.35g, 50mmol) in methanol (lOcm3) added dropwise.
The whole mixture was stirred over the weekend. A white precipitate was filtered off and the filtrate concentrate to give an oily residue.
The residue was di~solved in water and acidified with dilute HCL. The aqueous mixture was extracted into ethyl acetate and the extract washed, :
.

- 47 - 2~37~
dried and concentrated to give an oil which was purified by preparative TLC. After trituration with pentane a white solid was obtained.
H NMR (CDCl3): 1.55[(6H,s,C(CH3)23, 2.25(3H,s,CH3-C=N), 7-35 (4H,m,aromatic C--H), 8.90(1H,s,NH or OH).

This example illustrates the preparation of Compound No. 79 in Table Compound No. 80 prepared as described in Example 20, (0.249g, 9.2mmol) was dissolved in dry DMF (5cm3) and 1,2-dibromoethane (0.52g, 27.6mmol) added dropwise, followed by potassium carbonate ~0.26g, 18.4mmol). The resulting mixture was stirred overnight. The reaction mixture was diluted with water and extracted with ethyl acetate. The extract was washed, dried and concentrated to give a viScous yellow oil. Trituration with pentane gave the desired compound as a white solid that was filtered off and dried.

lH NMR (CDC13): 1.55(SH,s,C(CH3)2), 2.25(3H,s,(CH3-C-N), 4.20(4H,dt,2xCH2(0CH2CH20), 7.30(4H, m, aromatic C H).

This example illustrates the preparation of N,N-Dimethyl-2-chloroacetophenoneoxime-O-Isobutyrothioamide (Compound No. 89 in Table 1).
To a solution of the N,N,Dimethyl-2-chloroacetophenoneoxime-0-iso-butyramide (0.29g, 1.03mmol) in dry toluene (lOcm3) was added Lawesson's Reagent (0.416g, 1.03mmol) and the resulting mixture stirred and refluxed for 7 hours. The mixture was then concentrated to give a yellow oil residue which was applied to preparative TLC plates (silica, eluant: Et20 (l)/Hexane(l)).
The relevant band (top) was isolated to give the desired product as a yellow viscous oil.
lH NMR (CDCl3): 1.0(6H,s,c(CH3)2), 2.24(3H,s,CH3-C-N), 3.47(3H,s,CH3 of N(CH3)2, 3.56(3H,s,CH3 of N(CH3)2, 7.3(4H,m,aromatic C-H).

2 ~

The following compounds were prepared by method analogous to those described in Example 22:
N,N-Dimethyl-2-Fluoroacetophenone oxime-0-isobutyrothioamide. (Compound No. 90 in Table 1) - yellow viscous oil, structure confirmed by n.m.r.
N,N-Dimethyl-2-Bromoacetophenoneoxime-0-isobutyrothioamide. (Compound No.
91 in Table 1) - yellow viscous oil structure confirmed by n.m.r.
N,N-Dimethyl-2-Bromoacetophenone oxime-0-methoxacetamide (Compound No. 132 in Table 1) - oil structure confirmed by n.m.r.

The following Example was prepared by methods analoguos to those set out in Example 2 modified as necessary. In all cases the structure was confirmed by n.m.r.
Methyl-2-3-difluoroacetophenoneoxime-0-isobutyrate (Compound No. 92 in Table 1) oil.
Compound No. 93 in Table 1 - yellow oil.
Methyl-3,5-bis-trifluoromethylacetophenone oxime-0- isobutyrate (Compound No. 94 in Table 1) oil, that solidified on standing.
Methyl-2,3-dichloroacetophenoneoxime-0-isobutyrate (Compound No. 95 in Table 1). oil, which on standing and trituration with pentane gave a crystalline solid.
Methyl-2,5-dichloroacetophenone oxime-0-isobutyrate (Compound No. 96 in Table 1) oil.
Compound No. 97 in Table 1 - oil Methyl-2,6-dichloroacetophenone oxime-0-isobutyrate (Compound No. 98 in Table 1) - oil Methyl-2-chloro-6-fluoroacetophenone oxime-0- isobutyrate (Compound No. 99 in Table 1) oil . (Except that in the method 2-chloro,6-fluoroacetophenone oxime was used instead of the 2-chloroacetophenoneoxime).
Compound No. 101 in Table 1 (except that methyl ethyl ketone and K2C03 was used instead of NaH/DMS0).
Compound No. 103 in Table 1 - oil (except that 2-butanone and K2C03 was used instead of NaH/DMS0).
Methyl-2-Nitroacetophenone oxime-0-isobutyrate (Compound No. 104 in Table 1) - viscous oil.

'~ .

_ 49 _ 2 ~f~ 2 [2-Nitroacetoacetophenone oxime was used instead of 2-Chloroacetophenone oxime].
Methyl-trifluoroacetophenone oxime-0-isobutyrate (Compound No. 105 in Table 1) - oil.
Methyl-2-chloroacetophenone oxime-0-propionate (Compound No. 106 in Table 1) - oil. Methyl-2-bromopropionate is as used instead of methyl-~-bromoisobutyrate.
Methyl-2-chloroacetophenone oxime-0-methoxy-acetate. (Compound No. 107 in Table 1) [except THF was used instead of DMS0].
Methyl-2-aminoacetophenone oxime-0- isobutyrate. (Compound No. 108 in Table 1 - oil.
Compound No. 144 in Table II - (equimolar amounts of starting materials and NaH used).
Compound No. 120 in Table 1 - (equimolar amounts of star~ing materials and NaH used with no heating at all).
Compound No. 121 in Table 1 - (equimolar amounts of starting materials used, with no heating).
Compound No. 122 in Table 1 - (equimolar amounts of starting materials with no heating).
Compound No. 123 in Table 1 - (equimolar amounts of starting materials used with no heating).
Compound No. 124 in Table 1 - (equimolar amounts of starting materials used with no heating).
Compound No. 125 in Table 1 - (equimolar amounts of all reagents without heat)~
Compound No. 126 in Table 1 - (equimolar amounts of all reagents heated to 60C for 6 hours).
Compound No. 127 in Table 1.
Compound No. 128 in Table 1.
Compound No. 129 in Table 1.

The following compounds were prepared by a method analogous to that described in Example 3 step a.
Compound No. 100 in Table 1 - semi-solid. 1H NM~ (CDCl3):
1.65(6H,s,C(CH3)2), 7.15(3H,m,aromatic C-H), 8.45(1H,s,-CH=N-0).

_ 50 _ 2 ~ ~~. 3 ~
Compound No. 102 in Table 1 - semi-solid. 1H NMR (CDCl3): 1.65ppm (6H,s,c(CH3~2), 7.25-7.70(4H,m,aromatic C-H), 8.55(1H,s,-CH=N-0).

Biological Data The herbicidal properties of compounds of the invention was tested as described below.
Each compound was formulated for test by mixing an appropriate amount of it with 5ml of an emulsion prepared by diluting 160ml of a solution containing 21.8 grams per litre of Span 80 and 78.2 grams per litre of Tween 20 in methylcyclohexanone to 500ml with water. Span ~0 is a Trade Mark for a surface-active agent cornprising sorbitan monolaurate. Tween 20 is a Trade Mark for a surface-active agent comprising a condensate of 20 molar proportions of ethylene oxide with sorbitan monolaurate. The mixture of the compound and the emulsion was then shaken with glass beads and diluted to 40ml with water. The spray composition so prepared was sprayed on to young pot plants (post-emergence test) of the species named in Table 2 below, at a rate of equivalent to 1000 litres per hectare. Damage to plants was assessed 14 days after spraying by comparison with untreated plants, on a scale of 0 - 5 where 0 is 0 to 20% damage and 5 is complete kill. In the table of results a dash (-) means that no test was made.
A test was also carried out to detect pre-emergence herbicidal activity. Seeds of the test species were placed on the surface of fibre trays of soil and were sprayed with the compositions at the rate of 1000 litres per hectate. The seeds were then covered with further soil. Three weeks after spraying, the seedlings in the sprayed fibre trays were compared with the seedlings in unstrayed control trays, the damage being assessed on the same scale of 0 to 5.
The results of the tests are given in Table IV and V below, where Table IV shows the results on the 0-5 scale and Table V shows the results on a percentage scale.

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TABLE VI
Sb Sugar beet Rp Rape Ct Cotton Sy Soya bean Mz Maize Ww Winter wheat Rc Rice Sn Senecio vulgaris Ip Ipomoea purpurea Am Amaranthus retroflexus Pi olygonum aviculare Ca Chenopodium album Po Portulaca oleracea Xa Xanthium spinosum Ab Abutilon theophrastii Cv Convolvulus arvensis Ot/Av Oats ~cultivated in pre-emergence test and Avena fatua (wild oats) in post-emergence test~
Dg Digitaria sangiunalis Pu Poa annua Al Alopecuris myosuroides St Setaria viridis Ec Echinochloa crus-galli Sh Sorghum halepense Ag Agropyron repens Cn Cyperus rotundus Ga Galium aparine Am Amaranthus retroflexus Bd Bidens pilosa Eh Euphorbia heterophylla Xs Xanthium strumarium Ce Cyperus esculentes ..

- 64 - 20~ 7~
CHEMICAL FORMULAE
(in description) I N - O - C -R (I) Rl R

_ ~ (X)p(CH~)m (i) (CH2)n R13 R12 (ii) 0~ Rll N

~ N-O-H (II) Rl R3 H-NR~R9 ~VII) Z - 1- R4 (III) R5 AlR16R17R18 (~I) R~
~ o (IV) Rl R9R8N - Al R16R17 (V) - ~ . : . .

Claims (10)

1. A compound of formula (I):

(I) where R1 is alkyl, optionally substituted aryl or optionally substituted heterocyclyl;
R2 is hydrogen, optionally substituted lower alkyl, lower alkoxy, cycloalkyl, haloalkyl, lower thioalkyl, halo or cyano; or the group R1 is a group of sun formula (i):

(i) where q is 0 or an integer of from 1 to 4 and groups R6 are selected independently from hydroxy, alkyl, alkoxy, alkylcarbonyl, halogen, nitrile, nitro, haloalkyl and haloalkoxy; X is oxygen or sulphur, p is 0 or 1, n is 0 or 1 and m is 1, 2 or 3 provided that when n is 0, p+ m is 2 or 3 and when n is 1, p+ m is 1 or 2;
R3 and R4 are independently selected from hydrogen, halo, alkyl or alkoxy or R3 and R4 together with the carbon atom to which they are attached form a carbocyclic ring; and R5 is CN; CO2R7 where R7 is hydrogen, a cation or an esterifying group; a group -CYNR8R9 where Y is oxygen or sulphur and R8 and R9 are independently selected from hydrogen, hydroxy, alkyl or alkoxy or together with the nitrogen atom to which they are attached form a heterocyclic ring; or R8 together with R3 and the group to which it is attached form a heterocyclic ring, or R5 is a group of sub formula (ii) (ii) where R10, R11, R12 and R13 are independently selected from hydrogen or alkyl; or a group S(O)r R14 where r is 0, 1 or 2 and R14 is hydroxy, lower alkyl or aryl.

2. A compound according to claim 1 where R3 and R4 are other than hydrogen.

3. A compound according to claim 1 or claim 2 where R5 is a group CYNR8R9.

4. A compound according to claim 3 where Y is oxygen.

5. A compound according to any one of claims 1 to 4 where R1 is optionally substituted phenyl.

6. A compound according to claim 5 wherein the phenyl ring R1 has at least one substitutuent at the ortho position on the ring.

7. A herbicidal composition comprising a compound of formula (I) as defined in claim 1 in combination with an agriculturally acceptable carrier or diluent.

8. A composition according to claim 7 which further comprises another herbicidal compound.

9. A method of killing or controlling unwanted plants which methyl comprises applying to the plants or to the locus thereof an effective amount of a compound of formula (I) as defined in claim 1.

10. A process for preparing a compound of formula (I) as defined in claim 1 which process comprises reacting a compound of formula (II):
(II) wherein R1 and R2 are as defined in relation to formula (I); with a compound of formula (III):

(III) wherein R3, R4 and R5 are as defined in relation to formula (I) and Z
is a leaving group in the presence of a base; and thereafter if desired coverting the group R5 to a different such group.