CA1233824A - Biologically active amide derivatives - Google Patents
Biologically active amide derivativesInfo
- Publication number
- CA1233824A CA1233824A CA000523062A CA523062A CA1233824A CA 1233824 A CA1233824 A CA 1233824A CA 000523062 A CA000523062 A CA 000523062A CA 523062 A CA523062 A CA 523062A CA 1233824 A CA1233824 A CA 1233824A
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- alkyl
- compound
- alkoxy
- halogen
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Abstract
A B S T R A C T
INTERMEDIATES FOR BIOLOGICALLY ACTIVE AMIDE
DERIVATIVES
Compounds of the formula:
wherein A is hydrogen, bromine or chlorine;
B is -CN where A is hydrogen and is -CONH2 where A is chlorine or bromine;
and wherein R1 is a C1-5 alkyl radical or a C3-5 alkenyl radical or a C1-5 alkyl or C3-5 alkenyl radical substituted with one or more substituents selected from C1-4 alkoxy, C1-4 alkylthio and halogen;
a phenyl or naphthyl radical or a phenyl or naphthyl radical substituted with one or more substituents selected from halogen, C1-4 alkoxy, methylenedioxy, ethylenedloxy, C1-4 alkyl, C1-4 haloalkyl, nitro and cyano;
a benzyl radical or benzyl radical substituted in the phenyl ring with one or more substitutents selected from halogen, C1-4 alkoxy, C1-4 alkylthio, nitro, cyano, C1-4 haloalkyl and C1-4 alkyl;
a furyl, benzfuryl, thienyl, pyridyl, thiazolyl or benzthlazolyl radical optionally substituted with one or more substituents selected from halogen, C1-4 alkoxy, methylenedioxy, ethylenedioxy, C1-4 alkyl, C1-4 alkylthlo, C1-4 haloalkyl, nitro and cyano; or a heterocyclylmethyl radical in which the heterocyclyl radical is a furyl, benzfuryl, thienyl, pyridyl, thiazolyl or benzthiazolyl radical optionally substituted with one or more substituents selected from halogen, C1-4 alkoxy, methyldnedloxy, ethylenedloxy, C1-4 alkyl, C1-4 alkylthio, C1-4 haloalkyl, nitro and cyano.
INTERMEDIATES FOR BIOLOGICALLY ACTIVE AMIDE
DERIVATIVES
Compounds of the formula:
wherein A is hydrogen, bromine or chlorine;
B is -CN where A is hydrogen and is -CONH2 where A is chlorine or bromine;
and wherein R1 is a C1-5 alkyl radical or a C3-5 alkenyl radical or a C1-5 alkyl or C3-5 alkenyl radical substituted with one or more substituents selected from C1-4 alkoxy, C1-4 alkylthio and halogen;
a phenyl or naphthyl radical or a phenyl or naphthyl radical substituted with one or more substituents selected from halogen, C1-4 alkoxy, methylenedioxy, ethylenedloxy, C1-4 alkyl, C1-4 haloalkyl, nitro and cyano;
a benzyl radical or benzyl radical substituted in the phenyl ring with one or more substitutents selected from halogen, C1-4 alkoxy, C1-4 alkylthio, nitro, cyano, C1-4 haloalkyl and C1-4 alkyl;
a furyl, benzfuryl, thienyl, pyridyl, thiazolyl or benzthlazolyl radical optionally substituted with one or more substituents selected from halogen, C1-4 alkoxy, methylenedioxy, ethylenedioxy, C1-4 alkyl, C1-4 alkylthlo, C1-4 haloalkyl, nitro and cyano; or a heterocyclylmethyl radical in which the heterocyclyl radical is a furyl, benzfuryl, thienyl, pyridyl, thiazolyl or benzthiazolyl radical optionally substituted with one or more substituents selected from halogen, C1-4 alkoxy, methyldnedloxy, ethylenedloxy, C1-4 alkyl, C1-4 alkylthio, C1-4 haloalkyl, nitro and cyano.
Description
1~3~
BIOLOCICALLY ACTIVE AMIDE DERIVATIVES
_ This application is a division of Serial No. 397,435 filed March 2, 1982.
This invention relates to substituted benzamide derivatives useful as herbicides and fungicides, to processes of combatting weeds and fungal infestations and to herbicidal and fungicidal compositions.
Substituted benzamide derivatives have previously been proposed for use as herbicides, by way of example, the compounds disclosed in UK Patent Specifications No.1209608 and 1395802 may be mentioned.
According to the present invention, there are provided amide derivatives of the formula (I) Rl- C - N - CH -XR3 ~2 E
(I) wherein Rl is an optionally substituted alkyl, alkenyl, aryl, heterocyclyl, benzyl, or heterocyclylmethyi radical;
R2 is hydrogen, or an optionally substituted alkyl, alkenyl, benzyl, or heterocyclylmethyl, radical, X is oxygen, sulphur, or an -NH- group' R3 is an optionally substituted alkyl or alkenyl radical when X is oxygen or sulphur, or is an optionally substituted alkanoyl radical when X is -NH-, and E is a -CN, -CONH2, -CSNH2, or -CoNR4R5 group wherein each R4 and R5 is hydrogen or an optionally substituted alkyl or alkenyl group.
..a
BIOLOCICALLY ACTIVE AMIDE DERIVATIVES
_ This application is a division of Serial No. 397,435 filed March 2, 1982.
This invention relates to substituted benzamide derivatives useful as herbicides and fungicides, to processes of combatting weeds and fungal infestations and to herbicidal and fungicidal compositions.
Substituted benzamide derivatives have previously been proposed for use as herbicides, by way of example, the compounds disclosed in UK Patent Specifications No.1209608 and 1395802 may be mentioned.
According to the present invention, there are provided amide derivatives of the formula (I) Rl- C - N - CH -XR3 ~2 E
(I) wherein Rl is an optionally substituted alkyl, alkenyl, aryl, heterocyclyl, benzyl, or heterocyclylmethyi radical;
R2 is hydrogen, or an optionally substituted alkyl, alkenyl, benzyl, or heterocyclylmethyl, radical, X is oxygen, sulphur, or an -NH- group' R3 is an optionally substituted alkyl or alkenyl radical when X is oxygen or sulphur, or is an optionally substituted alkanoyl radical when X is -NH-, and E is a -CN, -CONH2, -CSNH2, or -CoNR4R5 group wherein each R4 and R5 is hydrogen or an optionally substituted alkyl or alkenyl group.
..a
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~ len the group R1 is an optionally substituted alkyl or alkenyl radical, it may be for example Cl 5 alkyl or C3_5 alkenyl radical. Examples of substituents include C1-C4 alkoxy, Cl-C4 alkylthio and halogen (i.e.
fluorine, chlorine, bromine or iodine).
~ en Rl is a benzyl radical optionally substituted in the phenyl ring, examples of substituents include halogen (fluorine, chlorine, bromine or iodine), Cl-C4 alkoxy, Cl C4 alkylthio, nitro, cyano, Cl-C4 haloalkyl (e.g. CF3), and Cl-C4 alkyl (e.g. CH3).
There may be from one to five substituents, which may be the same or dif~erent.
When Rl is an optionally substituted aryl group it may be a phenyl or naphthyl radical. Examples of substituents which may be present include fluorine, chlorine, bromine, iodine, Cl-C4 alkoxy, methylenedioxy and ethylenedioxy, Cl-C4 alkyl, Cl-C4 alkylthiot Cl-C4 haloalkyl (e.g. CF3) nitro and cyano. There may be from one to three or more substituents which may be the same or different. When Rl is a substituted phenyl radical the substituents are preferably in the 3, 4, or 5 positions. ~hen a methylenedioxy or ethylenedioxy substituent is present, it preferably is attached to the 3 and 4 positions of .he phenyl ring. A
halo~en substituent (e.g. Cl or Br) may also be present in the 4- or S-position, or both, in such compounds.
~ en Rl is an optionally substituted heterocyclyl radical, it may for example be a furyl, benzfuryl, thienyl, pyridyl, thiazolyl, or benzthiazolyl radical. E~amples of substituents which may be present include those listed above for the case when Rl is a substituted phenyl radical.
There may be from one to three or more substituents which may be the same or different.
~ihen Rl is an optionally substituted heterocyclylmethyl radical, the heterocyclyl qroup may be
~ len the group R1 is an optionally substituted alkyl or alkenyl radical, it may be for example Cl 5 alkyl or C3_5 alkenyl radical. Examples of substituents include C1-C4 alkoxy, Cl-C4 alkylthio and halogen (i.e.
fluorine, chlorine, bromine or iodine).
~ en Rl is a benzyl radical optionally substituted in the phenyl ring, examples of substituents include halogen (fluorine, chlorine, bromine or iodine), Cl-C4 alkoxy, Cl C4 alkylthio, nitro, cyano, Cl-C4 haloalkyl (e.g. CF3), and Cl-C4 alkyl (e.g. CH3).
There may be from one to five substituents, which may be the same or dif~erent.
When Rl is an optionally substituted aryl group it may be a phenyl or naphthyl radical. Examples of substituents which may be present include fluorine, chlorine, bromine, iodine, Cl-C4 alkoxy, methylenedioxy and ethylenedioxy, Cl-C4 alkyl, Cl-C4 alkylthiot Cl-C4 haloalkyl (e.g. CF3) nitro and cyano. There may be from one to three or more substituents which may be the same or different. When Rl is a substituted phenyl radical the substituents are preferably in the 3, 4, or 5 positions. ~hen a methylenedioxy or ethylenedioxy substituent is present, it preferably is attached to the 3 and 4 positions of .he phenyl ring. A
halo~en substituent (e.g. Cl or Br) may also be present in the 4- or S-position, or both, in such compounds.
~ en Rl is an optionally substituted heterocyclyl radical, it may for example be a furyl, benzfuryl, thienyl, pyridyl, thiazolyl, or benzthiazolyl radical. E~amples of substituents which may be present include those listed above for the case when Rl is a substituted phenyl radical.
There may be from one to three or more substituents which may be the same or different.
~ihen Rl is an optionally substituted heterocyclylmethyl radical, the heterocyclyl qroup may be
3 12~
for example a furyl, thienyl, pyridyl, thiazolyl or ben~thiazolyl group. Examples of substituents w~ich may be present in the heterocyclyl group include those described above for the case when Rl is a substituted phenyl radical.
R2 is preferably hydrogen but when it is not, then it may be an optionally substituted alkyl group, for example an Cl-C4 alkyl group. Examples of substituents which may be present include fluorine, chlorine, bromine, iodine, and Cl-C4 alkoxy~ When R~ is an optionally substituted alkenyl group it may be for example an alkenyl group of from 3-5 carbon atoms. Examples of substituents which may be present include those listed above for the case when R2 is an alkyl group.
~7hen R2 is an optionally substituted benzyl group, the substituents may include those described above for the case when Rl is substituted benzyl.
When R2 is an optionally substituted heterocyclyl methyl group, the heterocyclyl ring may be for example a furyl, thienyl, pyridyl, thiazolyl, or benzothiazolyl ring. Substituents which may be present include those described above for the case where Rl is a substituted phenyl radical.
When R3 is an optionally substituted alkyl or alkenyl radical it may have any of the values described above for the group R2.
When R3 is an alkanoyl group (i.e. when X is NH) it may for example have from 1 to 4 carbon ato~s (e.g. it may be a formyl, acetyl, or propionyl group).
-//
el,
for example a furyl, thienyl, pyridyl, thiazolyl or ben~thiazolyl group. Examples of substituents w~ich may be present in the heterocyclyl group include those described above for the case when Rl is a substituted phenyl radical.
R2 is preferably hydrogen but when it is not, then it may be an optionally substituted alkyl group, for example an Cl-C4 alkyl group. Examples of substituents which may be present include fluorine, chlorine, bromine, iodine, and Cl-C4 alkoxy~ When R~ is an optionally substituted alkenyl group it may be for example an alkenyl group of from 3-5 carbon atoms. Examples of substituents which may be present include those listed above for the case when R2 is an alkyl group.
~7hen R2 is an optionally substituted benzyl group, the substituents may include those described above for the case when Rl is substituted benzyl.
When R2 is an optionally substituted heterocyclyl methyl group, the heterocyclyl ring may be for example a furyl, thienyl, pyridyl, thiazolyl, or benzothiazolyl ring. Substituents which may be present include those described above for the case where Rl is a substituted phenyl radical.
When R3 is an optionally substituted alkyl or alkenyl radical it may have any of the values described above for the group R2.
When R3 is an alkanoyl group (i.e. when X is NH) it may for example have from 1 to 4 carbon ato~s (e.g. it may be a formyl, acetyl, or propionyl group).
-//
el,
4 1~3~8~4 R4 an~ R5 are preferably hydrogen, but when they arenot, they may be optionally substituted alkyl or alkenyl group it may have any of the values defined above for the group R2 when it is an optionally substituted alkyl or alkenyl radical.
Within the above definition, one sub-class of compounds according to the invention comprises those compounds whexein R2 is hydrogen. ~ithin this sub-class, a further sub-class comprises those compounds in which E
is a cyano group, X is O or S, and ~3 is Cl-C~ alkyl A group within the latter sub-class includes those compounds in which R1 is phenyl or heterocyclyl. Within the latter group, a sub-group includes compounds in which the heterocyclyl or phenyl group is substituted, for example by alkyl, alkoxy, methylenedioxy, or halogen, for example fluorine or chlorine. In such compounds the groups or atoms are preferably located in the 3, 4 or 5 positions of the phenyl ring.
The structural formula (I) given above is believed to be the one which best represents the structure of the compounds. For some compounds within the scope of the formula (I) it may be possible in principle for tautomeric forms of the compound to exist, in which a hydrogen atom is transposed to another part of the molecule and the chemical bonds between the atoms of the molecule are consequently re-arranged; thus, where ~1 is hydrogen, it is possible in principle for the molecule to exist in the alternative form (II) ~ C N C -- ~R3 ~/" I I
OH CN
(II) r) J~d~
~ le structura] formula (I) is intended to represent and include such tautomeric forms, insofar as they may exist. The structural formula (I) is also intenc~ed to include any physically clistinguishable modifications of the compounds which rnay arise, for example, from different ways in which the molecules are arranged in a crystal lattice, or Erom the inability of parts of the molecules to rotate freely in relation to other parts, or from geometrical and or optical isomerism, or from intra-molecular or inter-molecu].ar boncling, or otherwise.
Particular examples of compounds according to the invention are listed in Tab ~ _ -c~ ~
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. __ - -
Within the above definition, one sub-class of compounds according to the invention comprises those compounds whexein R2 is hydrogen. ~ithin this sub-class, a further sub-class comprises those compounds in which E
is a cyano group, X is O or S, and ~3 is Cl-C~ alkyl A group within the latter sub-class includes those compounds in which R1 is phenyl or heterocyclyl. Within the latter group, a sub-group includes compounds in which the heterocyclyl or phenyl group is substituted, for example by alkyl, alkoxy, methylenedioxy, or halogen, for example fluorine or chlorine. In such compounds the groups or atoms are preferably located in the 3, 4 or 5 positions of the phenyl ring.
The structural formula (I) given above is believed to be the one which best represents the structure of the compounds. For some compounds within the scope of the formula (I) it may be possible in principle for tautomeric forms of the compound to exist, in which a hydrogen atom is transposed to another part of the molecule and the chemical bonds between the atoms of the molecule are consequently re-arranged; thus, where ~1 is hydrogen, it is possible in principle for the molecule to exist in the alternative form (II) ~ C N C -- ~R3 ~/" I I
OH CN
(II) r) J~d~
~ le structura] formula (I) is intended to represent and include such tautomeric forms, insofar as they may exist. The structural formula (I) is also intenc~ed to include any physically clistinguishable modifications of the compounds which rnay arise, for example, from different ways in which the molecules are arranged in a crystal lattice, or Erom the inability of parts of the molecules to rotate freely in relation to other parts, or from geometrical and or optical isomerism, or from intra-molecular or inter-molecu].ar boncling, or otherwise.
Particular examples of compounds according to the invention are listed in Tab ~ _ -c~ ~
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~OTES
The abbreviations used in Table I are standard chemical symbols. Thus the symbols Me, Et, Pr and Ph stand for metnyl, et~yl, prop~l, and rhenyl groups respectively, and the symbols F5.C6. and 3-C1-5-~02.CGH3. r for example, stand for pentafluorophenyl and 3-chloro-5~nitxo-phenyl respectively.
Melting points are given ~or most compounds in the table~
~ere the compound is an oil, a refractive index measurement or nuclear magnetic resonance ~NMR) data are given in the ~otes below. In the NMR information, the symbols have the following meanings:-s singlet t triplet -- q quartet m multiplet d doublet Chemical shi~ts(S) are quote~ relative to tetramethyl-silane. The solvent used was deuterochloroform.
Notes for individual compounds follow:~
(a) Refractive index nD = 1.5233 (b) Refractive inde~ nO = 1.5197 (c) NMR data: S=1.3 (3H,t), 3.45 (3H,s), 3.7 (2H,q), 5.95 (H,S, broad), ca 7.5 (4H,m) (d) ~R data: ~=1.5 (6H,d), 2.35 (3H,s), 3.3 (3H,s), 4.1 (lH,m), 5.5 (lH,s), ca. 7.2 (aH,m).
?~
~e~ data: ~ =L.5 (6H,d), 2.35 (3E~s~, 3.3 (3H,s), 4.1 (l~,m), S.S (lH,s), ca.7.2 (4E~,m) f) NMR data: ~=1.3 (3H,t), 2.4 (3~,s), 3.7 (2H,q), 5.95 (lH,s,broad), ca. 7~3 (4H,m) g) N~R data: ~2.4 (3H,s), 3.1 (3H,s), 3.4 (3EI,s), ca. 6.1 (lH,s,very broad~, ca. 7.3 (4H,m) h) NMR data~ 3.1 (3His)/ 3.4 (3H,s), 6.1 ~s,v~ry broad), ca. 7.2 (4H,m).
i) MMR data: S=3.4 (3H,s), 4.75 (2H,s), 5.g (lH,s), ca. 7.3 (9H,m).
j) NMR data: ~=1.2 (3H,t), 3.55 (2H,q), 4.7 (2~,d), 5.95 (lH,broad), ca. 7.2 (8H,m).
X) NMR data: ~=3.35 (3H,s), 4.75 (2H,s1, 5.9 (lH,s,broad), ca. 7.2 (9H,m) 1) ~MR data^ ~=2.3 (6H,s), 3.3 (3H,s), 4.75 (2H,s) 5.9 (lH,s,broad), 7.0-7.4 (8H,m).
m) NMR data: ~=3.4 (3H,s), 4.75 (2H,s), 5.9 (lH,s,broad), ca. 6.8-7~3 (8H,m) ,,.,~
/
In another aspect the invention provid~s a process of inhibiting the growth of unwanted plants, which comprises applying to the plants, or to the locus thereof, a phyto-toxic amount of a compound of the formula (I) as hereinb~fore defined. The amount of the compound may vary, depending upon the identity of the particular compound chosen and the plant species whose growth i5 to be inhibited, but in general a~ounts of from 0.01 to 5.0 kilograms per hectare will be suitable: usually the amount will be from 0.2 to 1.O kilograms per hectare. The skilled worker in the herbicide art will readily be able to establish ~ppropriate application rates by standard procedures without undue experimentation.
The compounds of the invention are xelatively less toxlc towards certain crop plants than they are towards other plant species; accordingly, there is the possibility of using the compounds for selective weed control in these crops. Examples of such crops include cvtton, sugar beet, rape, lettuce, peas; the compounds may be useful in a number of crops of tl-e families Compositae and Leguminosae.
The compounds used in the process of the invention are preferably applied in the form of a composi~ion, 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 ~orm of dusting powders, or may take the form of granules. Suitable solid diluents include, for example, kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, and Fuller's Earth.
X
24 ~ 3.~
Solid cornposltions ~ay also be in the form of dispersible powders or grains comprising in additlon to the active ingredient, a wetting agent to facilitate the dispersion of the powder or grains in llquids. Such powders or ~rains may include fillers, suspending agents and the like.
Liquid compositions include aqueous solutions, dispersions and emulsions containing the active ingredient preferably in the presence of one or more surface active agents. ~1ater or organic liquids may be used to prepare ~olutions, dispersions, or emulsions ~f the active ingredient. The liquid composition~ o the ~nventio~ may also contain one or more corrosion inhibitors for example lauryl isoquinoliniwm bromide.
Sur~ace active agents may be of the cationic, anionic or non-ionic type. Suitable agents of the cationic type include for example quaternary a~monium compounds, for example cetyltrimethyl ammonium bromide. Suitable agents of the anionic type~nclude for example soaps, salts of aliphatic mono-esters of ~ulphurlc acid, for example sodium lauryl sulphate: and salts of sulphonated aromatic compounds, for example dodecyl~enzenesulphonate, sodium, calcium and ammonium lignosulphonate, butylnaphthalene sulphonate, and a m~xture of the sodium salts of diiso-propyl- and triisopropyl-naphthalenesulphonic acid.
Suitable agents of the non-ionic type include, for example, the condensation products of ethylene oxida with fatty alcohols SUCll as oleyl alcohol and cetyl alcohol, or with al~yl pllenols 3uch as octyl-phenol, nonylphenol, and octylcresol. Other non-ionic agents arc the partial esters derived from long chain fatty acids and hexitol anhydrides, for example sorbitol monolaurate the condensation products of the said partial esters witn ethylene oxide and the lecithins-2 S ~ h ~
The co~positions which are to be used in the form ofaqueous solutions, dispersions or e~uls~ons are generally supplied in the for~ of a concentrate contalnin~ a h~gh proportion of the act~ve ingredient, the concentrate being diluted with water before use. These concentrates are usually required to with3tana storage for prolonged periods and ater such stora~e to be capable of dilution with water in order to form aqueous preparatlons whlch remain homogenous for a sufficient time to enable them to be applied by conventional spray equip~ent.
The compositions of the lnvent~on may contain, in addition to carriers and surfac~-actlve agents, variou~
other constituents to increa~e their u~efulness. They may contain~ for example, buffer~ng salt~ to maintain the pH
of the co~position with~n a aesired range: antlfreeze agents, for example urea or propylene glycol: adjuvants, for example oils and humectants: ana sequestrants, for example citric acid and ethylenediam~netetracetic acid, which help to pre~ent the formatlon of insoluble precipitates when th~ co~po~itions are diluted with hard water. Aqueous dispersion~ may conta~n anti-settling agents and anti-caking agent~. The composi;tion~ may in general contain a dye or pigment to impart a characteristic colour. Agents for increa~ing viscosity may 2S be added to reduce the for~ation of fine droplet~ during spraying, and thereby reduce spray drift. Other additives useful for particular purposes will be known t~ those skilled in the formulation art.
In general concentrates may conveniently contain from 30 10 to 85% and preferably fro~ 25 to 60% by weight of active ingredient. Dilute preparations ready for use ~ay contain varying amounts of the active ingredient, depending upon the purpose for which they are to be used;
however, dilute preparations suitable for ~any uses 35 contain between 0.01~ and 10~ and preferably between 0.1 and 1~ by weisht of the active ingredient.
~!
2G ~.~3;~
The invention Eurt71er ~rov~des Frocess~s ~or prepar~ng compo~n~s oE Eormula ~I) above. Thus~ compounds ~Iherein R2 ~5 hyclrogen may be prepared, for example, by the proces~ of Scheme A below ~-Scheme A
(a) Rlcocl + NH2CH2CN --~ RlCoNHc~2c~T
~r (b3 (III) ~ brominating ag~nt ~ RlCONHC~CO~IH2 (IY~
(c) ~IV) ~ ~3XH , ~ RlCONHCH
\ CO~t2 ~V) (d) (V~ + dehydrating agent > RlCl~N~I--CII
\
CN
tVI) . ;.
. ~ ~
~ ~3;~
The process outlined in Scheme ~ begins with step (a), in whicll an acid chloride Rlcocl is reacted with amino-acetonitrile by a convent~onal procedure to obtain the acylamir,oacetonitrile der~vative (III). Thi3 is then reacted in step (b) w~th a brominating agent (for example bromine in glacial acetic acid) t~ gi~e the brominated derivative (IV). This brom1nation procedure also simultaneously hydrates the cyano group to a carbamoyl group -CONH2, and necessitates treatment with a dehydrating agent at a later stage to convert the carbamoyl group back into a cyano groupO It may be possible to avoid the undes;red converslon of the cyano group to carbamoyl by uYe of a different solvent or brominating agent and thereby shorten the process by mak~ng step (d) unnecessary.
In step (c), the bromo compound (IV3 i8 reacted with an appropriate alcvhol, th~ol, or amlde of formula R3XH
to obtain the carbamoyl compound (V). Preferably the reaction i5 carried out in a solvent; the solvent should be an aprotic solvent to avoid reaction of the solvent with the bromo-compound (IV). Preferably an acid acceptor i8 present in at least a 3toichiometric proportion.
Examples of acid acceptors include tertiary amines, for example triethylamine and pyr~dine. The reaction takes place readily even at ambient temperatures but may be accelerated if deRired by heating for example to lOO~C or above.
The intermediate compounds of formula IV and V are novel and constitute a further aspect of the present invention.
~ le final step (d) of Scheme ~ is the treatment of the carbamoyl compound (V) with a dehydrating agent to convert it to the corresponding cyano compound. The dehydrating agent may be, for example, a bi-molar amount of p-toluene 3S sulphonyl chloride in pyridine as solvent and acid acceptor, or another dehydrating agent, for example 2~
phosphorus o~ychloride-climethylformamide. The reac~ion with p-toluenesulphonyl chloride proceeds readily at ambient temperature. Scheme A has been described in terms of brominated compounds; however, the scheme could equally he carried out using a chlorinating agent (e.g.
gaseous chlorine) in place of a brominating agent, to produce the chlorinated compound corresponding to compound (IV), this could then be used in step (c) in place of compound (IV). This rou~e cannot be used where Rl is readily attacked by elemental bromine or chlorine.
A further process for making compounds of the invention in which R2 is hydrogen is ou~lined in Scheme B :-Scheme B
(a) RlCONH2 + HCO-C02R6-~ RlCONH-CH(OH)C02R6 (VII) (b) (VII) + SOC12~ RlcONHcH(cl~c02R6 (VIII) (c) (VIII) + R3XH - -~ RlCONHCH
\ CO2R6 (R3) (IX) (d) (IX) + ~3 ~ (V) 29 1 ~3~R~
In step (a) of Scheme B, an amide RlCONH2 is condensed with a glyoxylic ester HCO-C02R6 to give the hydroxy intermediate (VII). The group R6 is an ester radical, for example an alkyl group of 1 to 4 carbon atoms (e.g. a methyl group). In step (b), the hydroxy intermediate (VII) is treated with a chlorinatina aaent (e.g. thionyl chloride) to convert it to the chloro-derivative (VIII). This is in turn reacted in step (c) with the appropriate alcohol, thiol, or amine R3XH to give the ester (IX)o Treatment of this with ammonia in step (c) gives the carbamoyl derivative (V) which may then be converted to the cyano compound of the invention by the method of step (d) of Scheme A.
An alternative process for preparing the amide derivatives of the invention when X=0 in formula I is a variation of the Scheme B process above. This Scheme B
variation is outlined below :
OH
(a) RlCONH2 ~ HCOCOOR6__~ RlCONH~CHCOOR6 (VII) OH
(b) RlCONH-CHCOOR6 (VII) ~ HXR3 ¦ (H2S04 present as / catalyst) X~3 ~G//
RlCONHCH
\ (IX) (c) RlCONHCH + NH3~ RlCONHCH
\ COOR6 COMH2 (V) ) NH3 RlCONHCH
CN
(VI) In this modified Scheme B procedure it can be seen that one can proceed directl~r from the hydroxy intermediate (VII) to the ester (IX~ in one step. The ester ~IX) is then treated with ammonia, as in step d, to S produce the carbamoyl derivative ~V) which in turn is converted to the cyano compound of the Invention (VI) by means of the final step ~step d) of the process of Scheme A.
i ,,// , .
~ ~ ................. _ , .
31 ~33~
A further process for preparirlg compounds of the invention in which the group XR3 is an -N~-COZ group where Z is an alkyl or alkylene radical is outlined in Scheme C below.
Scheme C
. . ~
NHCOZ
(a) RlCONHCH(Br)CONH2 ~ ZCN AcetiC Rl~ON~CH
acid, (IV) (X) / NHCOZ
(b~ (X) dehydrating ~ Rl- CONHCH
agent CN
(XI) According to Scheme C the bromo-amide (IV) (prepared as in Scheme A) is reacted with the appropriate nitrile ZCN in acetic acid under the conditions of the Ritter reaction to give the amide (X). This is then treated with a dehydrating agent (e.g. trifluoroacetic anhydride in pyridine) to give the requirecl nitrile (XI).
A further method of preparing the nitriles (XI) is shown in Scheme D below .
3~
Scheme D
OH NHCO~
.
(a) RlCONHCH ~ ZCN acet~c aCidJRlCONHCH
\ H2SO4 (VII) (XII) (b) ~XII) ~ NH3 - ~ (X) dehydrating~ (XI) agent .
In Scheme D~ the hydroxy-ester (VII) prepared as in Scheme B is reacted with the appropriate nitrile ZCN in the pre~ence of acetic acid and sulphuric acid (Ritter reaction~ to give the amide (XII). This may then be reacted with ammonia to give the amide (X) already prepared in Scheme C. As in Scheme C the amide ~X) may then be dehydrated to give the required nitrile (XI). The conversion of (XII) to (X) may be troublesome because the esters (XII) tend to be highly insoluble.
A further method of preparing compounds of the invention is outlined in Scheme E.
Scheme E
-(a) RlCONHR2 (i)NaH RlCON -CH
(ii)R3X~CH~Br)C02R6 ~XIII) .. .
~3~
(b) (XIII) + NH3 . ~ RlCON CH
12 \
(XIV) (c) (XIV) ~ d ~ RlCO~ - CH
agent 12 R CN
~XV) According to Scheme E, an amide RlCONHR2 i5 first treated with sod ium hydride and the an~on so generated is then reacted with an alpha bromo ester R3X-CH~Br)CO2R6 to give the ester (XIII). Thi5 is then reacted with ammonia to give the amide (XIV), and finally (XIV~ is treated with a dehydrating agent to give the ni~rile (XV).
Thi8 method may ~onveniently be used to prepare compound6 in which R2 is other than hydrogen, particularly when either Rl or R2 is susceptible to reaction with bromine or sulphuryl chloride, which are used as reagents in certain other routes described herein.
A further method for preparing compounds of the invention is outlined in Scheme F.
Scheme F
(a~ R2NH2 + HOCH2CN ~ R2NHCH2CN
(b) R2NHCH2CN + RlCOCl------~ RlCONCH2CN
¦ (XVI~
'X!
3~
(c) (XVI) + 502C12 ~ CON- Cil (or Br2~ L 12 \ C~
(XVII) (d) (XVII) + HX~ _ ~ RlCOUCH
Base ¦ \
12 \
R CN
(XV) According to Scheme F, an amine R2NH2 is condensed with formaldehyde cyanhydrin to give the substituted amino-acetonitrile R2NHCH2CN. This is then acylated by theappropriate acid chloride RlCOCl tc, give the amide derivative (XVI).
This in turn is chlorina~ed ~e.g. with 502C12) or brominated (e.g. with Br2) to give the highly reactive bromo- or chloro-derivative (XVII~. This is treated with the appropriate alcohol, thiol or amlde ~3XH in the presence of base to give the required nitrile (XV).
T~le chloro- or hromo- nitriles (XVII) are too unstable to be isolated and characterised, and are used within a sllort time after they are prepared. The final stage (d) of the scheme may conveniently be carried out by using an excess of the alcohol, thiol, or amide ~3XH as solvent, and anhydrous potassium carbonate as the base.
Triethylamine or other tertiary amines may also be used as the base.
~1 ~3~
The cyanoamides (XVI~ may also be prepared by methods other than that described above. Thu9, the R2 substituent may be introduced by alkylation as ~hown below :-RlCONHCH2CN (i) N~ RlCONCH2CN (XVI) ~ R Br Another alternative is shown below :-RlCoNHR2 (i) NaH RlCONCH CN (XVI) ( i i ) ClCH2CN
Compounds of the invention in which the group E i8 a thiocarbamoyl radical may be prepared according to Scheme Gbelow :-Scheme G
RlCON--CH H2S ~ RlCON__CH
¦ ~ Pyridine/Et3N 1~ \
(XVIII) The reaction is conveniently carried out by passinggaseous H2S through a solution of the nitrile in pyridine containing a little triethylamine as catalyst. Usually the solution is externally cooled to 0-10. If the product does not separate from the solution, it may be isolated by removal of the solvent.
B~4 The amide derivatives of formula I, and compositions containing them, are variously active against a wide range of fungal diseases, particularly, for example, against:
Plasmopara viticola (downy mildew) on vines and Phytophthora infestans (late blight) on pot~toes and tomatoes and other species of Phytophthora Phytophthora parasitica, Phytophthora cinnamomi, Phytophthora ~ and Phyto~hthora capsici on a range of commercially important crops Peronospora tabacina on tobacco Peronospora para~itica on cabbage Peronospora destructor on onions Bremia lactuca on lettuce Pythium specie~ on a range of commercially importan~
crops Other fungal di~eases, for example:
Venturia inaequalis (scab) on apples Cercospora arachidicola on peanuts and other Cercospora species.
A particularly valuable feature of the activity of the amide derivatives i8 their systemic effect, i.e. their ability to move in a plant to combat an infection or infestation remote from the site of initial application.
Thus a derivative, or a composition containing it, may be applied to the soil surrounding the roots of a plant or to the seed or to other plant area~, e.g. leave~, and be taken up by the plant through Its roots, or other areas, to combat fungi locelly or elnewher~ _ // ' /
In another aspect, therefore, the invention provides a process for combatt-ing fungi, especially of inhibiting the growth of fungi on plants, which comprises applying to the plant~, or the locus thereof, a fun~icidally effective amount of a compound of the formula (I) as hereinbefore defined. The amount of the compound may vary, depending upon the identity of the particular compound chosen, the fungal species whose growth is to be inhibited, and the plant or locus involved.
The skilled worker in the fungicide art will readily be able to establish appropriate application rates by standard proeedure~ without undue experimentation.
Preferred compounds for use in the fungicidal compositions of the invention and the process for combatting fungi are those defined in detail above with reference to formula I wherein R2 i9 hydrogen, Rl is optionally-substituted phenyl, or heterocyclyl, for example 2-furyl, X is 0 or S (X is preferably 0) and R3 is alkyl, alkenyl, or haloalkyl, and E is CN or CSNH2.
Preferred phenyl substitution, when Rl is phenyl, is at the 3, 4 or 5 positions and is alkyl, alkoxy, methylenedioxy or halogen. Preferred alkyl groups for R3 are Cl_4 alkyl. Allyl is also a preferred group for R3.
The compounds used in the process and compositions 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 fungicidal 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-actlve agent. ~
-~, 3~
The amide derivatives l~ay ~)e used as such for anti-fungal purposes but are more conveniently formulated into compositions for such usage.
The invention also provides fungicidal compositions S comprising as active ingredient an amide derivative as defined in any of the paragraphs above.
The amide derivatives and compositions containing them can be used to combat plant fungi and treat plants or seeds in a number of ways, for example -they can be applied, formulated or unformulated, directly to the foliage of a plant which is infected or likely to become infected, or they can be applied also to bushes and trees, to soil or to other medium in which plants, bushes or trees are growing or to ba planted, or they can be sprayed on, dusted on or applied as a cream or paste formulation. Application can be to any part of the plant, bush or tree, for example to the foliage, stems, branches, seeds or roots, or to the soil surrounding the roots.
The terms "combatting" and "treatment" as used herein embrace all the foregoing modes of ap~lication and the term "plant" includes seedlings, bushes and trees.
Furthermore, the method of the invention includes protectant, prophylactic and eradicant treatment.
The derivatives are preferably used for agricultural and horticultural purposes in the form of compositions.
The type of composition used in any instance will depend upon the particular purpose envisaged.
The compositions may be in the form of dustlng powders or granules, for example ordinary grains or "slow release"
granules wherein the active ingredient is mixed with a solid diluent or carrier, for example, kaolin, bentonite, kieselguhr, dolomite, calcium carbondte, talc, powdered magnesia, Fuller's earth, gypsum, Hewitt's earth, diatomaceous earth and China clay.
Compositions Eor dressing seed ~ay, f~r example, comprise an agent (for example a mineral oil) for assisting the adhesion of the co~positlon to the seed.
The compositions may also be in the for~ of S dispersible powders or grains comprising a wetting agent to facilitate the dispersion in liquids af the powder or grains which may contain also fillers and suspending agents.
The aqueous dispersion of emulsions may be prepared by dissolving the active ingredient~s~ in an orqanic solvent which may contain wetting, dispersina or emulsifying agent(s) and then addlng the mixture so obtained to water which may also contain wetting, dispersing or em~lsifying agent~s). Suitable organic solvents are ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, xylenes and trichloroethylene.
The compositions for spraying may also be in the form of aerosols wherein the formulation is held in a propellant, e.g. fluorotrichloromethane or dichloro-difluoromethane.
By including suitable additives, for exa~ple additives for irnproving the distribution, adhesive power and resistance to rain on treated surfaces, the different cornpositions can be better adapted for various uti-lities.
The derivatives can be used in smoke generators and also as mixtures with fertilisers (e.g. nitrogen- or phosphorus- containing fertilisers). Compositions comprising only granules oE fertiliser incorporating, for example coated with, the derivative, are preferred.
The invention therefore also provides a fertiliser cornDosition comprising the derivative and a fertiliser.
The compositions mav also be in the form of liquid preparations for use as dips or sprays which are generally aqueous dispersions or emulsions containing the active ingredient in the presence of one or more surface " ~a~3;3~2,~
active agent(s), dispersing agent(s), emulsifying agent(s) or anionic or non-ionic agents. Suitable cationic aaents are quaternary ammonium compounds for example, cetyltrimethylammonium bromide.
Suitable anionic agents are soaps, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), and salts of sulphonated aromatic compounds (for example sodium dodecylbenzene-sulphonate, sodium, calcium or ammonium lignosulphonate, butylnaphthalene ~ulphonate, and a mixture of sodium di-isopropyl- and triisopropylnaphthalene sulphonates).
Suitable non-ionic agents are the condensation products of ethylene oxide with fatty alcohol~ such as oleyl alcohol or cetyl alcohol, or with alkyl phenols such as octylphenol, nonylphenol and octylcresol. Other non-ionic agents are the partial esters derived from lony chain fatty acids and hexitol anhydrides, the condensation products of the said partial esters with ethylene ocide, and the lecithins. Suitable suspending agents are hydrophilic colloids (for example polyvinylpyrrolidone and sodium carboxymethylcellulose), and the vegetable gums ~for example gum acacia and gum tragacanth).
The compositions for use as aqueous dispersions or emulsions are generally supplied in the form of a concentrate containing a high proportion of the active ingredient(s), the concentrate to ~e diluted with water before use. These concentrates often should be able to withstand storage for prolonged periods and after such form aqueous preparations which remain homogenous for a sufficient time to enable them to be applied by conventional spray equipment. T~le concentrates may conveniently contain 10-85%, generally 25-60~, by weight of the active ingredient(s).
~7hen diluted to form aaueous preparations, such preparations may contain varying amounts of the active ingredient(s) depending upon the intended purpose, but an aqueous preparation containing 0.0005% or 0.01~ to 10~ by weight of active insredient(s) may be used.
4 ~
The co~positions of this invention can co~prise also other compound( 5 ) having bioloyical activity, e.g.
compounds having similar or complemen~axy fungicidal or plant growth regulating activity or compounds ha~ing herbicidal or insecticidal activity.
The other fungicidal co~pound can be for example one which is capable o combating ear diseases of cereals (e.g.
wheat) such as Septoria, Gibberella and Relminthosporium spp., seed and soil borne di.seases and downy and powdery ~ildews on grapes and powdery mildew and scab on apple etc.
These mixtures of fungicides can have a broader spectrum of activity than the compound of general formula II) alone;
furt~er the other fungicide can have a synergistic effect of the fungicidal actiYity of the compound of general lS formula (I). Examples of the other fungicidal compound are imazalil, benomyl, carbendazim (BCM), thiophanate-methyl, captafol, captan, sulphur, dithiocarbamates, carbathiins, copper oxychloride, triforine, dodemorph, tridemorph, dithianon, pyrazophos, binapacryl, quinomethionate, panoctine, furalaxyl, aluminium tris(ethylphosphonate~, DPX3217* ethirimol, dimethirimol, b~pirimate, chlorothalonil and metazanine.
Suitable insecticides are pirimorS croneton, dimethoate, metasystox and formothion.
The other plant growth regulating compound can be one which controls weeds or seedhead for~ation, improves the level or longevity of the plant growth resulating activity of the compounds of general formula ~I), selectively controls the growth of the less desirable plants (e.g.
grasqes) or causes the compound of general for~ula (I) to act faster or slower as a plant growth reaulating agent.
Some of these other agents wîll be herbicides. Examples of suitable agents are the gibberellins (e.g. GA3, GA4 or GA7), the auxins (e.g. indoleacetic acid, indolebutyric acid, naphthoxyacetic acid or naphthylacetic acid), the cytokinins (e.g. kinetin, diphenylurea, benzimidazole, benzyladenine or BAP), phenoxyacetic acids (e.g. 2,4-D or ~Reg Trade Mark , 4~. 3L~3~3~
MCPA), substituted benzoic acids (e.g. TIBA~, morphactins (e.g. chlorfluorecol), maleic hydrazide, glyphosate, glyphosine, long chain fatty alcohols and acids (e.g. Off Shoot O*or Off Shoot ~ , dikegulac, Sustar* Embark*
substituted quaternary ammonium and phosphonium compounds (e.g. CC~ or Phosfon-D~, Ethrel, carbetamide, Racuza, Alar, asulam, abscissic acid, isopyrimol, RH531~, hydroxy-benzonitriles (e.g. bromokynil), Avenge, Sufix or Lontrel.
Th~ invention is illustrated by the following Examples, in which unless otherwise stated all parts are by weight and temperatures in dPgrees Centigrade. The Examples that describechemical syntheses give details in some cases o the nuclear magnetic resonance ~NMR) spectra of the compound~. The information given is the chemical shift (S) for each peak in the spectrum together with a symbol to indicate the nature of the peak, as follows :- s(singlet);
d(doublet); m(multiplet); c(quartet) J t(triplet). The solvent used was fully deuterated dimethyl sulphoxide or deuterochloroform (CDC13).
EXAMPLE
.
This Example illustrates the preparation of com~pound no.4 of Table I by the process of Scheme A.
(a) Preparation of Benzoylamino(bromo)acetamide To a suspension of benzoylaminoacetonitrile (5 g) in stirred glacial acetic acid (50 ml) was added all at once bromine (5.0 9). After a brief induction period, the bromine colour was discharged and the product (5.8 g) precipitated from the acetic acid. The product was filtered off, washed with glacial acetic acid, and then with ~ anhydrous ether, and dried. A sample crystallised from ~lacial acetic acid had m.p. 157 (dec.).
... .~.
8,.."4 Found: C, 42.22; H, 3.7; N, 10.81 CgHgBrN202 reauires : C, 42.02; H, 3.5, N, 10.89~.
~b) Preparation of Benzoylamino~ethoxy)acetamide The foregoing bromoamide (13.4 g) was suspended in anhydrous ethanol (50 ml) and heated on a steam bath just long enough for it to dissolve (ca. 5 min), whereupon the solution was cooled. 'Fhe ethanol was removed under vacuum and the residual heavy oil was dissolved in water (40 ml) and neutralised by the cautious addition of solid sodium bicarbonate. 'Fhe solution was then extracted with chloro-form (200 ml) and the dried (~IgS04) extract evaporated to yield a white solid. Crystallisation of this from dichloro-methane-hexane gave the product (7.7 g), m.p. 148-150.
Found: C, 59.19; H, 6.27; N, 12.5 CllH14M203 requires : C, S9.45; H, 6.34; N, 12.6% ~(DMS0 d6): 1.15 (t, 3H), 3.55 (q, 2H), 5.55 (d, lH), 7.2~8.0 (m, 7H~, 9.0 (d, lH).
(c) Preparation of Benzoylamino(ethoxy)acetonitrile (Compound No. 4) A solution of the foregoing ethoxyamide (5.55 g) in anhydrous pyridine (40 ml) containing p-toluenesulphonyl chloride (4.78 g) was kept at room temperature for 72 hours. The reaction mixture was diluted with water (200 ml) and the precipitated solid filtered off, washed with water and dried. Crystallisation of the soli~ from carbon tetracnloride gave the product (2.5 g), m.p. 107-llG.
Found: C, 64.31, H, 6.3, N, 13.54 CllH12 4 'I o.~ ~3~
requires : C, 64.69; H, 5.92; N, 13.71~ S(C~CL3): 1.25 ~t, 3H), 3.8 (q, 2H), 6.3 (d, lH), 7~a-8.0 (m, 6H).
EXP~IPLE 2 This Example illustrates the preparation of compound no.38 of Table I by the process of Scheme B.
(a~
~hydroxy)] acetate 3-Methoxybenzamide (13.25 g) and methyl glyoxylate (7.72 g) in toluene ~150 ml) were heated under reflux in a ~ean-Stark apparatus for 6 hours. On cooling the mixture the product separated and was crystallised from toluene.
Yield, 12.0 g, m.p. 93-94.
Found: C, 55.45, H, 5.37 N, 6.3 CllH13~O5 requires : C, 55.23; H, 5.43; N, 5.85~.
(b) Preparation of ~-Methoxybenzoylamino(ethoxy)acetamide The foregoing ester (5.0 g) and thionyl chloride (40 ml) were stirred together for 2 hours., after which the excess of thionyl chloride was removed under vacuum. The residue was dissolved in ethanol (100 ml) and the solution .hen ev~porated under vacuum. The residual oil was treated wiLh aqueous ammonia (d 0.88) and the mixture allowed to stand.
The solid so formed was filtered off, dried, and crystallised from chloroform-light petroleum to give the product (1.8 g), m.p. 143-144.
round: C, 56.17; H, 6.49; ~`7~ 10.73 C12~16N2 4 ,~5 ~L~23~
requires : C, 57.14, H, 6.35; N, 11.11% S(~MSo-d6):
1.3 (t, 3~), 3.7 (q, 2H), 4.0 (s, 3H), 5.7(d,1H), 7.2-7.8 (m, 6H), 9.15 (d, 1~).
(c) Preparation of 3-Methoxybenzoylamino(ethoxy) acetonitrile The foregoing ethoxyamide ~1.0 g), p-toluenesulphonyl chlorlde (1.28 g) and pyridine (20 ml) were allowed to stand at room temperature or 72 hrs. The reaction was then worked up as described in paragraph (c) of Example 1.
The product (0~7 g) was crystaliised from chloroform-light petroleum and had m.p. 72.
~(CDC13) : 1.2 (t, 3H), 3.7 (q, 2H), 3.8 (s, 3H), 6.2 (d, lH), 7-7.6 (m, SH).
This Examp:Le illustrates the preparation of compound no. 53 of Table 1, using the process of Scheme F.
Preparation of N-Methylbenzoylamino(methoxy)acetonitrile ,__.... .. .
To a cooled (5--10) and stirred solution of ~-methyl-benzoylaminoacetonitrile (5.0 g) in anhydrous carbon tetrachloride (75 ml) was added dropwise bromine (4.6 g).
Following the addltion the mixture was stirred for a further 5 min. at room temperature, when methanol (2S ml) was added all at once. After stirring the mixture for 2 further 5 min., triethylamine (5.81 g) was added to the mixture. The solution was then washed with water and the organic phase dried (MgS04) and evaporated. The residual oil was chromatographed on a dry silica column usina ether-hexane (7:3) as an eluen~. Separation o. the major oand from the colu~n gave the product as a colourless oil ~1.0 g) n21 1.5233.
D
~6 123;~
~ (CDC13): 3.1 (s, 3H), 3.4 (s, 3H), 6.0 (very broad, lH~, 7.4 (s, 5H).
_ This Example illustra~es the preparation of compound no.40 of Table I, using the process of Scheme A.
(a) Preparation of 3-Chlorobenzoylamino(methylthio?-acetamide To a solution of 3-chlorob~nzoylamino(bromo)aceta~ide ~5.5 g) in anhydrous tetrahydrofuran ~100 ml) containing methyl mercaptan (slight excess) W2S added 1 equivalent of triethylamine and the mixture kept for 72 hrs. The solution was filtered and the filtrate evaporated to give an oll which solidified on treatment with ether.
Crystallisation of the solid from ethyl acetate gave the product (0-67 g).
lS ~ (~MS0-d6): 2.06 (s, 3H), 5.6 (d, lH), 7.4-7.8 (m, 6H), 8.9 and 9.2 (two doublets, lH).
(b) Preparation of 3-chlorobenzoylamino(methylthio)-acetonitrile (Compound No.40) The foregoing amide (0.67 g) and 2 equivalents of p-toluenesulphonyl chloride in pyridine (10 ml) were kept atroom temperature for 48 hrs. The mixture was then poured into water (100 ml). The solid which separated was dried, and crystallised from chloroform-light petroleum to give the product (0.1 g), m.p. 115-117.
Found: C, 48.99; H, 3~71; N, 11.01 CloHgClN2OS
requires : C, 49.9; H, 3.77; N, 11.64~
5 (C~C13): 2.35 (s, 3H), 6.05 (d, lH~, 7.8-7.2 (m, 5H).
This Example illustrates the preparation of compound no 158 of Table 1 by the process of Scheme C.
(a) Preparation of Acetylamino(3,5-dimethylbenzoylamino) acetamide To a suspension of 3,5-dimethylbenzoylaminoacetonitrile (1 g) in glacial a~etic acid (20 ml) was added all at once bromine (0.85 g). After stirring the mixture at room temperature for 15 min. the white solid was separated, washed with anhydrous ether and then re-suspended in glacial acetic acid (10 ml). To this was added concentrated sulphuric acid (1.5 ml) and acetonitrile (8 ml). After 1 hour the mixture was poured intG water (30 ml) and extracted with chloroform (2 x 30 ml). The dried (MgS043 extract was evaporated and the residue crystallised frc)m aqueous ethanol to give the product (Q.38 g) as a white solid (Compound No 154 of Table I), 20 m.p. 244-5 Q .
Found: C, 58.49, H, 6.42; M, 15.46 C13H17N3O3 requires : C, 59.13: H, 6.46; M, 15.g7%
~ (DMSO-d6): 1.9 (3H,s), 2.3 (6H,s), 5.8 (lH,dd), C2.
7.1-7.5 (5H,m), 8.3 (lH,d), 8.7 (lH,d).
(b) Preparation of Acetylamino (3,5-dime~hylbenzoylamino) .
acetonltrile The foregoing acetamide ( 1. O c ) w2s dissolved in anhydrous ~8 pyridine (25 ml) which was then cooled to -25.
Trifluoroacetic anhydride ~1.5 g) was added dropwise to the cooled and stirred solution, and following the addition the solution was allowed to come to 0 whereupon it was poured into water (70 ml) and extracted with ether (2 x 50 ml). Evaporation of the ethereal extracts and crystallisation of the residue from ethyl acetate-hexane gave the product (0.6 g) as a pale cream solid, mOp. 195-7o.
Found: C, 62.51; H, 5.98; N, 17.16 C13H15N302 requires : C, 63.67; H, 6.12; N, 17.14%
~ (DMS0-d6) : 1.8 ~3H,s), 2.2 (6H,s), 6.2 (lH,dd~, 7.1 (l~,s), 7.4 (2H,s), 9.1 (lH,s), 9.5 (lH,s).
EXAMPL~ 6 This Example illustrates the preparation of compound no.153 of Table I by ',he process of Scheme D.
(a) Preparation of Methyl Acetylamino (3,5-dichlorobenzoylamino) acetate .
A mixture of 3,5-dichlorobenzamide (19.0 g) and methyl glyoxylate (8.8 g) in ethyl acetate (300 ml) was heated under reflux for 8 hours. The solvent was removed and the residual adduct was crystallised from chloroform-light petroleum. A portion (4.0 g) of the adduct was dissolved in a mixture of glacial acetic acid (30 ml) and acetonitrile (10 ml) with stirring, and then concentrated sulphuric acid (4 ml) was added. The mixture was kept at room temperature overnight when water (100 ml) was added.
The precipitated solid was washed with water, dried, and crystallised 'rom ethanol to give the product (2.45 g) as a colourless crystalline solid, m.p. 235-237.
3 ~ L~
Found: C, 45.24; Il, 3-88, N, 8.84 C12H12C12N2O4 requires : C, 45.14; H, 3-76, N, 8.77~
S(~MSO-d6) : 1.95 13H,s), 3.7 (3H,s), 5-9 (lH,dd) t 7-95 (3H,m), 8.9 (lH,d), 9~75 (lH,d).
(b) Preparation of Acetvlamino (3,5~dichlorobenzoylamino) acetamide The foregoing ester (1.46 g~ was dissolved in dimethylformamide (70 ml) which was then saturated with ammonia (gas) and the mixture kept for 7 days. The solvent was removed under reduced pressure and the residue crystallised from aqueous dimethylformamide to give the product (0~72 g), m.p. 267-268 (dec).
Found: C, 43.62; H, 3.72; N, 13.82 CllHllC12N303 requires : C, 43.42, H, 3.62; N, 13.82%
~ (~MSO-d6): 1.95 (3H,s), 5.9 (lH,dd), 7.3 (2H,d,broad) 7.6 (lH,m), 7.9 (2H,m), 8.35 (lH,d), 9.2 (lH,d).
(c) Preparation of Acetylamino (3,5-dichloroben~ovlamino) acetonitrile _ The foregoing acetamide (0.5 g~ in anhydrous pyridine (10 ml) at -25 was treated with trifluoroacetic anhydride as described above. The product (0~18 g), crystallised from aqueous dimethylformamide, had m.p. 227-228.
Found: C~ 45.95; H, 3.12; N, 14.43 Cl1HgC12N3O2 reauires : C, 46.15; H, 3.15; N, 14.68%
,~ ISO-d6): 1.95 (3H,s), 6.4 (lH,dd), 7.9 (3H,m), 9.35 (lH,d), 10.0 (lH,d).
5 (~ p ~ r~
EXA~PLE 7 This Example illustrates the preparation of compound no.159 of Table I bv the process of Scheme E.
(a) N-Furfuryl-3,5-dichlorobenæamide To a vigorously stirred solution of furfurylamine ~2.78 g) in ethyl acetate (40 ml) was added sodium hydroxide (1.15 g) in water (45 ml), followed immediately by the addition of a solution of 3,5-dichlorobenzoyl chloride (6.0 g) in ethyl acetate (20 ml). Following the mild exothermic reaction the ethyl acetate layer was removed, dried (MgS04), and evaporated. Crystallisation of the residue from cyclohexane gave the product ~6.6 g) as colourless needles.
(b) Preparation of N-Furfurvl-3,5-dichlorobenzoylamino ~ , . , _ _ (methoxy) acetonitrile To a stirred suspension of sodium hydride (0.58 g) in anhydrous tetrahydrofuran (40 ml) was added in portions the foregoing a~ide (3.0 g). Following the addition and cessation of hydrogen evolution was added with stirring methyl 2-bromo-2-methoxy acetate (2.04 g) and the mixture stirred for a further 2 hours at room temperature. Water (100 ml) was then acded and the solution extracted with methylene chloride (3 x 50 ml) and the extracts dried and evaporated. The resultant crude oily ester was dissolved in methanol (20 ml) which was then saturated with ammonia gas and kept overnight. The solvent was removed under reduced pressure and the residual oil triturated with ether to give crude amide (1.91 g). The crude amide (1.75 g) was dissolved in anhvdrous pyridine (10 ml), cooled to 51 1~3~3~4 0~ with stirring and phosphorus oxychloride ~0.84 g) added dropwise so that the temperature of the mixture did not exceed 0. After 25 minu~es at 0, water (100 ml) was added and the mixture was extracted with ether (40 ml).
The dried (MgS04) ether extract was chromatographed on silica using diisopropyl ether as the eluent. Following elution from the column and evaporation of th~ solvent the product (1.24 g) was obtained as a colourless oil which slowly crystallised, m.p. 89-90.
~ (CDC13): 3.4 (3H,s), 4.65 (2H,s), 6.1 (lH,s,broad)
Uo N ~ O ~ U~D O I I S
~ ~ OO I / ~, u u u ~ n u I ~I ~ \ U S(J '~
/ ~/ I I ~ r y u u O O O ~N rl ~ U~ N NO N N ~N
C~ .__ 2~, ~33~
__ _~
E~
~o a Zo _ - __ C~ .,.
r _l ~ ~ ~
~0 ~ ~
~ ~ .~: m m m ~ :Z; Z Z Z Z Z
..
u X o o o o o o <S:
_ _ P~ ~
a) N ~ ~) ~D
I ~D ~ O O C,) O
) 10 0 C~
I t~ ~1 ! ~ `
u7 1 0 a~~ I
Z
O o u~ a)~ O
:~. Z; O O O O O
~ ~ ~ .~
C.~
2~
~OTES
The abbreviations used in Table I are standard chemical symbols. Thus the symbols Me, Et, Pr and Ph stand for metnyl, et~yl, prop~l, and rhenyl groups respectively, and the symbols F5.C6. and 3-C1-5-~02.CGH3. r for example, stand for pentafluorophenyl and 3-chloro-5~nitxo-phenyl respectively.
Melting points are given ~or most compounds in the table~
~ere the compound is an oil, a refractive index measurement or nuclear magnetic resonance ~NMR) data are given in the ~otes below. In the NMR information, the symbols have the following meanings:-s singlet t triplet -- q quartet m multiplet d doublet Chemical shi~ts(S) are quote~ relative to tetramethyl-silane. The solvent used was deuterochloroform.
Notes for individual compounds follow:~
(a) Refractive index nD = 1.5233 (b) Refractive inde~ nO = 1.5197 (c) NMR data: S=1.3 (3H,t), 3.45 (3H,s), 3.7 (2H,q), 5.95 (H,S, broad), ca 7.5 (4H,m) (d) ~R data: ~=1.5 (6H,d), 2.35 (3H,s), 3.3 (3H,s), 4.1 (lH,m), 5.5 (lH,s), ca. 7.2 (aH,m).
?~
~e~ data: ~ =L.5 (6H,d), 2.35 (3E~s~, 3.3 (3H,s), 4.1 (l~,m), S.S (lH,s), ca.7.2 (4E~,m) f) NMR data: ~=1.3 (3H,t), 2.4 (3~,s), 3.7 (2H,q), 5.95 (lH,s,broad), ca. 7~3 (4H,m) g) N~R data: ~2.4 (3H,s), 3.1 (3H,s), 3.4 (3EI,s), ca. 6.1 (lH,s,very broad~, ca. 7.3 (4H,m) h) NMR data~ 3.1 (3His)/ 3.4 (3H,s), 6.1 ~s,v~ry broad), ca. 7.2 (4H,m).
i) MMR data: S=3.4 (3H,s), 4.75 (2H,s), 5.g (lH,s), ca. 7.3 (9H,m).
j) NMR data: ~=1.2 (3H,t), 3.55 (2H,q), 4.7 (2~,d), 5.95 (lH,broad), ca. 7.2 (8H,m).
X) NMR data: ~=3.35 (3H,s), 4.75 (2H,s1, 5.9 (lH,s,broad), ca. 7.2 (9H,m) 1) ~MR data^ ~=2.3 (6H,s), 3.3 (3H,s), 4.75 (2H,s) 5.9 (lH,s,broad), 7.0-7.4 (8H,m).
m) NMR data: ~=3.4 (3H,s), 4.75 (2H,s), 5.9 (lH,s,broad), ca. 6.8-7~3 (8H,m) ,,.,~
/
In another aspect the invention provid~s a process of inhibiting the growth of unwanted plants, which comprises applying to the plants, or to the locus thereof, a phyto-toxic amount of a compound of the formula (I) as hereinb~fore defined. The amount of the compound may vary, depending upon the identity of the particular compound chosen and the plant species whose growth i5 to be inhibited, but in general a~ounts of from 0.01 to 5.0 kilograms per hectare will be suitable: usually the amount will be from 0.2 to 1.O kilograms per hectare. The skilled worker in the herbicide art will readily be able to establish ~ppropriate application rates by standard procedures without undue experimentation.
The compounds of the invention are xelatively less toxlc towards certain crop plants than they are towards other plant species; accordingly, there is the possibility of using the compounds for selective weed control in these crops. Examples of such crops include cvtton, sugar beet, rape, lettuce, peas; the compounds may be useful in a number of crops of tl-e families Compositae and Leguminosae.
The compounds used in the process of the invention are preferably applied in the form of a composi~ion, 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 ~orm of dusting powders, or may take the form of granules. Suitable solid diluents include, for example, kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, and Fuller's Earth.
X
24 ~ 3.~
Solid cornposltions ~ay also be in the form of dispersible powders or grains comprising in additlon to the active ingredient, a wetting agent to facilitate the dispersion of the powder or grains in llquids. Such powders or ~rains may include fillers, suspending agents and the like.
Liquid compositions include aqueous solutions, dispersions and emulsions containing the active ingredient preferably in the presence of one or more surface active agents. ~1ater or organic liquids may be used to prepare ~olutions, dispersions, or emulsions ~f the active ingredient. The liquid composition~ o the ~nventio~ may also contain one or more corrosion inhibitors for example lauryl isoquinoliniwm bromide.
Sur~ace active agents may be of the cationic, anionic or non-ionic type. Suitable agents of the cationic type include for example quaternary a~monium compounds, for example cetyltrimethyl ammonium bromide. Suitable agents of the anionic type~nclude for example soaps, salts of aliphatic mono-esters of ~ulphurlc acid, for example sodium lauryl sulphate: and salts of sulphonated aromatic compounds, for example dodecyl~enzenesulphonate, sodium, calcium and ammonium lignosulphonate, butylnaphthalene sulphonate, and a m~xture of the sodium salts of diiso-propyl- and triisopropyl-naphthalenesulphonic acid.
Suitable agents of the non-ionic type include, for example, the condensation products of ethylene oxida with fatty alcohols SUCll as oleyl alcohol and cetyl alcohol, or with al~yl pllenols 3uch as octyl-phenol, nonylphenol, and octylcresol. Other non-ionic agents arc the partial esters derived from long chain fatty acids and hexitol anhydrides, for example sorbitol monolaurate the condensation products of the said partial esters witn ethylene oxide and the lecithins-2 S ~ h ~
The co~positions which are to be used in the form ofaqueous solutions, dispersions or e~uls~ons are generally supplied in the for~ of a concentrate contalnin~ a h~gh proportion of the act~ve ingredient, the concentrate being diluted with water before use. These concentrates are usually required to with3tana storage for prolonged periods and ater such stora~e to be capable of dilution with water in order to form aqueous preparatlons whlch remain homogenous for a sufficient time to enable them to be applied by conventional spray equip~ent.
The compositions of the lnvent~on may contain, in addition to carriers and surfac~-actlve agents, variou~
other constituents to increa~e their u~efulness. They may contain~ for example, buffer~ng salt~ to maintain the pH
of the co~position with~n a aesired range: antlfreeze agents, for example urea or propylene glycol: adjuvants, for example oils and humectants: ana sequestrants, for example citric acid and ethylenediam~netetracetic acid, which help to pre~ent the formatlon of insoluble precipitates when th~ co~po~itions are diluted with hard water. Aqueous dispersion~ may conta~n anti-settling agents and anti-caking agent~. The composi;tion~ may in general contain a dye or pigment to impart a characteristic colour. Agents for increa~ing viscosity may 2S be added to reduce the for~ation of fine droplet~ during spraying, and thereby reduce spray drift. Other additives useful for particular purposes will be known t~ those skilled in the formulation art.
In general concentrates may conveniently contain from 30 10 to 85% and preferably fro~ 25 to 60% by weight of active ingredient. Dilute preparations ready for use ~ay contain varying amounts of the active ingredient, depending upon the purpose for which they are to be used;
however, dilute preparations suitable for ~any uses 35 contain between 0.01~ and 10~ and preferably between 0.1 and 1~ by weisht of the active ingredient.
~!
2G ~.~3;~
The invention Eurt71er ~rov~des Frocess~s ~or prepar~ng compo~n~s oE Eormula ~I) above. Thus~ compounds ~Iherein R2 ~5 hyclrogen may be prepared, for example, by the proces~ of Scheme A below ~-Scheme A
(a) Rlcocl + NH2CH2CN --~ RlCoNHc~2c~T
~r (b3 (III) ~ brominating ag~nt ~ RlCONHC~CO~IH2 (IY~
(c) ~IV) ~ ~3XH , ~ RlCONHCH
\ CO~t2 ~V) (d) (V~ + dehydrating agent > RlCl~N~I--CII
\
CN
tVI) . ;.
. ~ ~
~ ~3;~
The process outlined in Scheme ~ begins with step (a), in whicll an acid chloride Rlcocl is reacted with amino-acetonitrile by a convent~onal procedure to obtain the acylamir,oacetonitrile der~vative (III). Thi3 is then reacted in step (b) w~th a brominating agent (for example bromine in glacial acetic acid) t~ gi~e the brominated derivative (IV). This brom1nation procedure also simultaneously hydrates the cyano group to a carbamoyl group -CONH2, and necessitates treatment with a dehydrating agent at a later stage to convert the carbamoyl group back into a cyano groupO It may be possible to avoid the undes;red converslon of the cyano group to carbamoyl by uYe of a different solvent or brominating agent and thereby shorten the process by mak~ng step (d) unnecessary.
In step (c), the bromo compound (IV3 i8 reacted with an appropriate alcvhol, th~ol, or amlde of formula R3XH
to obtain the carbamoyl compound (V). Preferably the reaction i5 carried out in a solvent; the solvent should be an aprotic solvent to avoid reaction of the solvent with the bromo-compound (IV). Preferably an acid acceptor i8 present in at least a 3toichiometric proportion.
Examples of acid acceptors include tertiary amines, for example triethylamine and pyr~dine. The reaction takes place readily even at ambient temperatures but may be accelerated if deRired by heating for example to lOO~C or above.
The intermediate compounds of formula IV and V are novel and constitute a further aspect of the present invention.
~ le final step (d) of Scheme ~ is the treatment of the carbamoyl compound (V) with a dehydrating agent to convert it to the corresponding cyano compound. The dehydrating agent may be, for example, a bi-molar amount of p-toluene 3S sulphonyl chloride in pyridine as solvent and acid acceptor, or another dehydrating agent, for example 2~
phosphorus o~ychloride-climethylformamide. The reac~ion with p-toluenesulphonyl chloride proceeds readily at ambient temperature. Scheme A has been described in terms of brominated compounds; however, the scheme could equally he carried out using a chlorinating agent (e.g.
gaseous chlorine) in place of a brominating agent, to produce the chlorinated compound corresponding to compound (IV), this could then be used in step (c) in place of compound (IV). This rou~e cannot be used where Rl is readily attacked by elemental bromine or chlorine.
A further process for making compounds of the invention in which R2 is hydrogen is ou~lined in Scheme B :-Scheme B
(a) RlCONH2 + HCO-C02R6-~ RlCONH-CH(OH)C02R6 (VII) (b) (VII) + SOC12~ RlcONHcH(cl~c02R6 (VIII) (c) (VIII) + R3XH - -~ RlCONHCH
\ CO2R6 (R3) (IX) (d) (IX) + ~3 ~ (V) 29 1 ~3~R~
In step (a) of Scheme B, an amide RlCONH2 is condensed with a glyoxylic ester HCO-C02R6 to give the hydroxy intermediate (VII). The group R6 is an ester radical, for example an alkyl group of 1 to 4 carbon atoms (e.g. a methyl group). In step (b), the hydroxy intermediate (VII) is treated with a chlorinatina aaent (e.g. thionyl chloride) to convert it to the chloro-derivative (VIII). This is in turn reacted in step (c) with the appropriate alcohol, thiol, or amine R3XH to give the ester (IX)o Treatment of this with ammonia in step (c) gives the carbamoyl derivative (V) which may then be converted to the cyano compound of the invention by the method of step (d) of Scheme A.
An alternative process for preparing the amide derivatives of the invention when X=0 in formula I is a variation of the Scheme B process above. This Scheme B
variation is outlined below :
OH
(a) RlCONH2 ~ HCOCOOR6__~ RlCONH~CHCOOR6 (VII) OH
(b) RlCONH-CHCOOR6 (VII) ~ HXR3 ¦ (H2S04 present as / catalyst) X~3 ~G//
RlCONHCH
\ (IX) (c) RlCONHCH + NH3~ RlCONHCH
\ COOR6 COMH2 (V) ) NH3 RlCONHCH
CN
(VI) In this modified Scheme B procedure it can be seen that one can proceed directl~r from the hydroxy intermediate (VII) to the ester (IX~ in one step. The ester ~IX) is then treated with ammonia, as in step d, to S produce the carbamoyl derivative ~V) which in turn is converted to the cyano compound of the Invention (VI) by means of the final step ~step d) of the process of Scheme A.
i ,,// , .
~ ~ ................. _ , .
31 ~33~
A further process for preparirlg compounds of the invention in which the group XR3 is an -N~-COZ group where Z is an alkyl or alkylene radical is outlined in Scheme C below.
Scheme C
. . ~
NHCOZ
(a) RlCONHCH(Br)CONH2 ~ ZCN AcetiC Rl~ON~CH
acid, (IV) (X) / NHCOZ
(b~ (X) dehydrating ~ Rl- CONHCH
agent CN
(XI) According to Scheme C the bromo-amide (IV) (prepared as in Scheme A) is reacted with the appropriate nitrile ZCN in acetic acid under the conditions of the Ritter reaction to give the amide (X). This is then treated with a dehydrating agent (e.g. trifluoroacetic anhydride in pyridine) to give the requirecl nitrile (XI).
A further method of preparing the nitriles (XI) is shown in Scheme D below .
3~
Scheme D
OH NHCO~
.
(a) RlCONHCH ~ ZCN acet~c aCidJRlCONHCH
\ H2SO4 (VII) (XII) (b) ~XII) ~ NH3 - ~ (X) dehydrating~ (XI) agent .
In Scheme D~ the hydroxy-ester (VII) prepared as in Scheme B is reacted with the appropriate nitrile ZCN in the pre~ence of acetic acid and sulphuric acid (Ritter reaction~ to give the amide (XII). This may then be reacted with ammonia to give the amide (X) already prepared in Scheme C. As in Scheme C the amide ~X) may then be dehydrated to give the required nitrile (XI). The conversion of (XII) to (X) may be troublesome because the esters (XII) tend to be highly insoluble.
A further method of preparing compounds of the invention is outlined in Scheme E.
Scheme E
-(a) RlCONHR2 (i)NaH RlCON -CH
(ii)R3X~CH~Br)C02R6 ~XIII) .. .
~3~
(b) (XIII) + NH3 . ~ RlCON CH
12 \
(XIV) (c) (XIV) ~ d ~ RlCO~ - CH
agent 12 R CN
~XV) According to Scheme E, an amide RlCONHR2 i5 first treated with sod ium hydride and the an~on so generated is then reacted with an alpha bromo ester R3X-CH~Br)CO2R6 to give the ester (XIII). Thi5 is then reacted with ammonia to give the amide (XIV), and finally (XIV~ is treated with a dehydrating agent to give the ni~rile (XV).
Thi8 method may ~onveniently be used to prepare compound6 in which R2 is other than hydrogen, particularly when either Rl or R2 is susceptible to reaction with bromine or sulphuryl chloride, which are used as reagents in certain other routes described herein.
A further method for preparing compounds of the invention is outlined in Scheme F.
Scheme F
(a~ R2NH2 + HOCH2CN ~ R2NHCH2CN
(b) R2NHCH2CN + RlCOCl------~ RlCONCH2CN
¦ (XVI~
'X!
3~
(c) (XVI) + 502C12 ~ CON- Cil (or Br2~ L 12 \ C~
(XVII) (d) (XVII) + HX~ _ ~ RlCOUCH
Base ¦ \
12 \
R CN
(XV) According to Scheme F, an amine R2NH2 is condensed with formaldehyde cyanhydrin to give the substituted amino-acetonitrile R2NHCH2CN. This is then acylated by theappropriate acid chloride RlCOCl tc, give the amide derivative (XVI).
This in turn is chlorina~ed ~e.g. with 502C12) or brominated (e.g. with Br2) to give the highly reactive bromo- or chloro-derivative (XVII~. This is treated with the appropriate alcohol, thiol or amlde ~3XH in the presence of base to give the required nitrile (XV).
T~le chloro- or hromo- nitriles (XVII) are too unstable to be isolated and characterised, and are used within a sllort time after they are prepared. The final stage (d) of the scheme may conveniently be carried out by using an excess of the alcohol, thiol, or amide ~3XH as solvent, and anhydrous potassium carbonate as the base.
Triethylamine or other tertiary amines may also be used as the base.
~1 ~3~
The cyanoamides (XVI~ may also be prepared by methods other than that described above. Thu9, the R2 substituent may be introduced by alkylation as ~hown below :-RlCONHCH2CN (i) N~ RlCONCH2CN (XVI) ~ R Br Another alternative is shown below :-RlCoNHR2 (i) NaH RlCONCH CN (XVI) ( i i ) ClCH2CN
Compounds of the invention in which the group E i8 a thiocarbamoyl radical may be prepared according to Scheme Gbelow :-Scheme G
RlCON--CH H2S ~ RlCON__CH
¦ ~ Pyridine/Et3N 1~ \
(XVIII) The reaction is conveniently carried out by passinggaseous H2S through a solution of the nitrile in pyridine containing a little triethylamine as catalyst. Usually the solution is externally cooled to 0-10. If the product does not separate from the solution, it may be isolated by removal of the solvent.
B~4 The amide derivatives of formula I, and compositions containing them, are variously active against a wide range of fungal diseases, particularly, for example, against:
Plasmopara viticola (downy mildew) on vines and Phytophthora infestans (late blight) on pot~toes and tomatoes and other species of Phytophthora Phytophthora parasitica, Phytophthora cinnamomi, Phytophthora ~ and Phyto~hthora capsici on a range of commercially important crops Peronospora tabacina on tobacco Peronospora para~itica on cabbage Peronospora destructor on onions Bremia lactuca on lettuce Pythium specie~ on a range of commercially importan~
crops Other fungal di~eases, for example:
Venturia inaequalis (scab) on apples Cercospora arachidicola on peanuts and other Cercospora species.
A particularly valuable feature of the activity of the amide derivatives i8 their systemic effect, i.e. their ability to move in a plant to combat an infection or infestation remote from the site of initial application.
Thus a derivative, or a composition containing it, may be applied to the soil surrounding the roots of a plant or to the seed or to other plant area~, e.g. leave~, and be taken up by the plant through Its roots, or other areas, to combat fungi locelly or elnewher~ _ // ' /
In another aspect, therefore, the invention provides a process for combatt-ing fungi, especially of inhibiting the growth of fungi on plants, which comprises applying to the plant~, or the locus thereof, a fun~icidally effective amount of a compound of the formula (I) as hereinbefore defined. The amount of the compound may vary, depending upon the identity of the particular compound chosen, the fungal species whose growth is to be inhibited, and the plant or locus involved.
The skilled worker in the fungicide art will readily be able to establish appropriate application rates by standard proeedure~ without undue experimentation.
Preferred compounds for use in the fungicidal compositions of the invention and the process for combatting fungi are those defined in detail above with reference to formula I wherein R2 i9 hydrogen, Rl is optionally-substituted phenyl, or heterocyclyl, for example 2-furyl, X is 0 or S (X is preferably 0) and R3 is alkyl, alkenyl, or haloalkyl, and E is CN or CSNH2.
Preferred phenyl substitution, when Rl is phenyl, is at the 3, 4 or 5 positions and is alkyl, alkoxy, methylenedioxy or halogen. Preferred alkyl groups for R3 are Cl_4 alkyl. Allyl is also a preferred group for R3.
The compounds used in the process and compositions 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 fungicidal 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-actlve agent. ~
-~, 3~
The amide derivatives l~ay ~)e used as such for anti-fungal purposes but are more conveniently formulated into compositions for such usage.
The invention also provides fungicidal compositions S comprising as active ingredient an amide derivative as defined in any of the paragraphs above.
The amide derivatives and compositions containing them can be used to combat plant fungi and treat plants or seeds in a number of ways, for example -they can be applied, formulated or unformulated, directly to the foliage of a plant which is infected or likely to become infected, or they can be applied also to bushes and trees, to soil or to other medium in which plants, bushes or trees are growing or to ba planted, or they can be sprayed on, dusted on or applied as a cream or paste formulation. Application can be to any part of the plant, bush or tree, for example to the foliage, stems, branches, seeds or roots, or to the soil surrounding the roots.
The terms "combatting" and "treatment" as used herein embrace all the foregoing modes of ap~lication and the term "plant" includes seedlings, bushes and trees.
Furthermore, the method of the invention includes protectant, prophylactic and eradicant treatment.
The derivatives are preferably used for agricultural and horticultural purposes in the form of compositions.
The type of composition used in any instance will depend upon the particular purpose envisaged.
The compositions may be in the form of dustlng powders or granules, for example ordinary grains or "slow release"
granules wherein the active ingredient is mixed with a solid diluent or carrier, for example, kaolin, bentonite, kieselguhr, dolomite, calcium carbondte, talc, powdered magnesia, Fuller's earth, gypsum, Hewitt's earth, diatomaceous earth and China clay.
Compositions Eor dressing seed ~ay, f~r example, comprise an agent (for example a mineral oil) for assisting the adhesion of the co~positlon to the seed.
The compositions may also be in the for~ of S dispersible powders or grains comprising a wetting agent to facilitate the dispersion in liquids af the powder or grains which may contain also fillers and suspending agents.
The aqueous dispersion of emulsions may be prepared by dissolving the active ingredient~s~ in an orqanic solvent which may contain wetting, dispersina or emulsifying agent(s) and then addlng the mixture so obtained to water which may also contain wetting, dispersing or em~lsifying agent~s). Suitable organic solvents are ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, xylenes and trichloroethylene.
The compositions for spraying may also be in the form of aerosols wherein the formulation is held in a propellant, e.g. fluorotrichloromethane or dichloro-difluoromethane.
By including suitable additives, for exa~ple additives for irnproving the distribution, adhesive power and resistance to rain on treated surfaces, the different cornpositions can be better adapted for various uti-lities.
The derivatives can be used in smoke generators and also as mixtures with fertilisers (e.g. nitrogen- or phosphorus- containing fertilisers). Compositions comprising only granules oE fertiliser incorporating, for example coated with, the derivative, are preferred.
The invention therefore also provides a fertiliser cornDosition comprising the derivative and a fertiliser.
The compositions mav also be in the form of liquid preparations for use as dips or sprays which are generally aqueous dispersions or emulsions containing the active ingredient in the presence of one or more surface " ~a~3;3~2,~
active agent(s), dispersing agent(s), emulsifying agent(s) or anionic or non-ionic agents. Suitable cationic aaents are quaternary ammonium compounds for example, cetyltrimethylammonium bromide.
Suitable anionic agents are soaps, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), and salts of sulphonated aromatic compounds (for example sodium dodecylbenzene-sulphonate, sodium, calcium or ammonium lignosulphonate, butylnaphthalene ~ulphonate, and a mixture of sodium di-isopropyl- and triisopropylnaphthalene sulphonates).
Suitable non-ionic agents are the condensation products of ethylene oxide with fatty alcohol~ such as oleyl alcohol or cetyl alcohol, or with alkyl phenols such as octylphenol, nonylphenol and octylcresol. Other non-ionic agents are the partial esters derived from lony chain fatty acids and hexitol anhydrides, the condensation products of the said partial esters with ethylene ocide, and the lecithins. Suitable suspending agents are hydrophilic colloids (for example polyvinylpyrrolidone and sodium carboxymethylcellulose), and the vegetable gums ~for example gum acacia and gum tragacanth).
The compositions for use as aqueous dispersions or emulsions are generally supplied in the form of a concentrate containing a high proportion of the active ingredient(s), the concentrate to ~e diluted with water before use. These concentrates often should be able to withstand storage for prolonged periods and after such form aqueous preparations which remain homogenous for a sufficient time to enable them to be applied by conventional spray equipment. T~le concentrates may conveniently contain 10-85%, generally 25-60~, by weight of the active ingredient(s).
~7hen diluted to form aaueous preparations, such preparations may contain varying amounts of the active ingredient(s) depending upon the intended purpose, but an aqueous preparation containing 0.0005% or 0.01~ to 10~ by weight of active insredient(s) may be used.
4 ~
The co~positions of this invention can co~prise also other compound( 5 ) having bioloyical activity, e.g.
compounds having similar or complemen~axy fungicidal or plant growth regulating activity or compounds ha~ing herbicidal or insecticidal activity.
The other fungicidal co~pound can be for example one which is capable o combating ear diseases of cereals (e.g.
wheat) such as Septoria, Gibberella and Relminthosporium spp., seed and soil borne di.seases and downy and powdery ~ildews on grapes and powdery mildew and scab on apple etc.
These mixtures of fungicides can have a broader spectrum of activity than the compound of general formula II) alone;
furt~er the other fungicide can have a synergistic effect of the fungicidal actiYity of the compound of general lS formula (I). Examples of the other fungicidal compound are imazalil, benomyl, carbendazim (BCM), thiophanate-methyl, captafol, captan, sulphur, dithiocarbamates, carbathiins, copper oxychloride, triforine, dodemorph, tridemorph, dithianon, pyrazophos, binapacryl, quinomethionate, panoctine, furalaxyl, aluminium tris(ethylphosphonate~, DPX3217* ethirimol, dimethirimol, b~pirimate, chlorothalonil and metazanine.
Suitable insecticides are pirimorS croneton, dimethoate, metasystox and formothion.
The other plant growth regulating compound can be one which controls weeds or seedhead for~ation, improves the level or longevity of the plant growth resulating activity of the compounds of general formula ~I), selectively controls the growth of the less desirable plants (e.g.
grasqes) or causes the compound of general for~ula (I) to act faster or slower as a plant growth reaulating agent.
Some of these other agents wîll be herbicides. Examples of suitable agents are the gibberellins (e.g. GA3, GA4 or GA7), the auxins (e.g. indoleacetic acid, indolebutyric acid, naphthoxyacetic acid or naphthylacetic acid), the cytokinins (e.g. kinetin, diphenylurea, benzimidazole, benzyladenine or BAP), phenoxyacetic acids (e.g. 2,4-D or ~Reg Trade Mark , 4~. 3L~3~3~
MCPA), substituted benzoic acids (e.g. TIBA~, morphactins (e.g. chlorfluorecol), maleic hydrazide, glyphosate, glyphosine, long chain fatty alcohols and acids (e.g. Off Shoot O*or Off Shoot ~ , dikegulac, Sustar* Embark*
substituted quaternary ammonium and phosphonium compounds (e.g. CC~ or Phosfon-D~, Ethrel, carbetamide, Racuza, Alar, asulam, abscissic acid, isopyrimol, RH531~, hydroxy-benzonitriles (e.g. bromokynil), Avenge, Sufix or Lontrel.
Th~ invention is illustrated by the following Examples, in which unless otherwise stated all parts are by weight and temperatures in dPgrees Centigrade. The Examples that describechemical syntheses give details in some cases o the nuclear magnetic resonance ~NMR) spectra of the compound~. The information given is the chemical shift (S) for each peak in the spectrum together with a symbol to indicate the nature of the peak, as follows :- s(singlet);
d(doublet); m(multiplet); c(quartet) J t(triplet). The solvent used was fully deuterated dimethyl sulphoxide or deuterochloroform (CDC13).
EXAMPLE
.
This Example illustrates the preparation of com~pound no.4 of Table I by the process of Scheme A.
(a) Preparation of Benzoylamino(bromo)acetamide To a suspension of benzoylaminoacetonitrile (5 g) in stirred glacial acetic acid (50 ml) was added all at once bromine (5.0 9). After a brief induction period, the bromine colour was discharged and the product (5.8 g) precipitated from the acetic acid. The product was filtered off, washed with glacial acetic acid, and then with ~ anhydrous ether, and dried. A sample crystallised from ~lacial acetic acid had m.p. 157 (dec.).
... .~.
8,.."4 Found: C, 42.22; H, 3.7; N, 10.81 CgHgBrN202 reauires : C, 42.02; H, 3.5, N, 10.89~.
~b) Preparation of Benzoylamino~ethoxy)acetamide The foregoing bromoamide (13.4 g) was suspended in anhydrous ethanol (50 ml) and heated on a steam bath just long enough for it to dissolve (ca. 5 min), whereupon the solution was cooled. 'Fhe ethanol was removed under vacuum and the residual heavy oil was dissolved in water (40 ml) and neutralised by the cautious addition of solid sodium bicarbonate. 'Fhe solution was then extracted with chloro-form (200 ml) and the dried (~IgS04) extract evaporated to yield a white solid. Crystallisation of this from dichloro-methane-hexane gave the product (7.7 g), m.p. 148-150.
Found: C, 59.19; H, 6.27; N, 12.5 CllH14M203 requires : C, S9.45; H, 6.34; N, 12.6% ~(DMS0 d6): 1.15 (t, 3H), 3.55 (q, 2H), 5.55 (d, lH), 7.2~8.0 (m, 7H~, 9.0 (d, lH).
(c) Preparation of Benzoylamino(ethoxy)acetonitrile (Compound No. 4) A solution of the foregoing ethoxyamide (5.55 g) in anhydrous pyridine (40 ml) containing p-toluenesulphonyl chloride (4.78 g) was kept at room temperature for 72 hours. The reaction mixture was diluted with water (200 ml) and the precipitated solid filtered off, washed with water and dried. Crystallisation of the soli~ from carbon tetracnloride gave the product (2.5 g), m.p. 107-llG.
Found: C, 64.31, H, 6.3, N, 13.54 CllH12 4 'I o.~ ~3~
requires : C, 64.69; H, 5.92; N, 13.71~ S(C~CL3): 1.25 ~t, 3H), 3.8 (q, 2H), 6.3 (d, lH), 7~a-8.0 (m, 6H).
EXP~IPLE 2 This Example illustrates the preparation of compound no.38 of Table I by the process of Scheme B.
(a~
~hydroxy)] acetate 3-Methoxybenzamide (13.25 g) and methyl glyoxylate (7.72 g) in toluene ~150 ml) were heated under reflux in a ~ean-Stark apparatus for 6 hours. On cooling the mixture the product separated and was crystallised from toluene.
Yield, 12.0 g, m.p. 93-94.
Found: C, 55.45, H, 5.37 N, 6.3 CllH13~O5 requires : C, 55.23; H, 5.43; N, 5.85~.
(b) Preparation of ~-Methoxybenzoylamino(ethoxy)acetamide The foregoing ester (5.0 g) and thionyl chloride (40 ml) were stirred together for 2 hours., after which the excess of thionyl chloride was removed under vacuum. The residue was dissolved in ethanol (100 ml) and the solution .hen ev~porated under vacuum. The residual oil was treated wiLh aqueous ammonia (d 0.88) and the mixture allowed to stand.
The solid so formed was filtered off, dried, and crystallised from chloroform-light petroleum to give the product (1.8 g), m.p. 143-144.
round: C, 56.17; H, 6.49; ~`7~ 10.73 C12~16N2 4 ,~5 ~L~23~
requires : C, 57.14, H, 6.35; N, 11.11% S(~MSo-d6):
1.3 (t, 3~), 3.7 (q, 2H), 4.0 (s, 3H), 5.7(d,1H), 7.2-7.8 (m, 6H), 9.15 (d, 1~).
(c) Preparation of 3-Methoxybenzoylamino(ethoxy) acetonitrile The foregoing ethoxyamide ~1.0 g), p-toluenesulphonyl chlorlde (1.28 g) and pyridine (20 ml) were allowed to stand at room temperature or 72 hrs. The reaction was then worked up as described in paragraph (c) of Example 1.
The product (0~7 g) was crystaliised from chloroform-light petroleum and had m.p. 72.
~(CDC13) : 1.2 (t, 3H), 3.7 (q, 2H), 3.8 (s, 3H), 6.2 (d, lH), 7-7.6 (m, SH).
This Examp:Le illustrates the preparation of compound no. 53 of Table 1, using the process of Scheme F.
Preparation of N-Methylbenzoylamino(methoxy)acetonitrile ,__.... .. .
To a cooled (5--10) and stirred solution of ~-methyl-benzoylaminoacetonitrile (5.0 g) in anhydrous carbon tetrachloride (75 ml) was added dropwise bromine (4.6 g).
Following the addltion the mixture was stirred for a further 5 min. at room temperature, when methanol (2S ml) was added all at once. After stirring the mixture for 2 further 5 min., triethylamine (5.81 g) was added to the mixture. The solution was then washed with water and the organic phase dried (MgS04) and evaporated. The residual oil was chromatographed on a dry silica column usina ether-hexane (7:3) as an eluen~. Separation o. the major oand from the colu~n gave the product as a colourless oil ~1.0 g) n21 1.5233.
D
~6 123;~
~ (CDC13): 3.1 (s, 3H), 3.4 (s, 3H), 6.0 (very broad, lH~, 7.4 (s, 5H).
_ This Example illustra~es the preparation of compound no.40 of Table I, using the process of Scheme A.
(a) Preparation of 3-Chlorobenzoylamino(methylthio?-acetamide To a solution of 3-chlorob~nzoylamino(bromo)aceta~ide ~5.5 g) in anhydrous tetrahydrofuran ~100 ml) containing methyl mercaptan (slight excess) W2S added 1 equivalent of triethylamine and the mixture kept for 72 hrs. The solution was filtered and the filtrate evaporated to give an oll which solidified on treatment with ether.
Crystallisation of the solid from ethyl acetate gave the product (0-67 g).
lS ~ (~MS0-d6): 2.06 (s, 3H), 5.6 (d, lH), 7.4-7.8 (m, 6H), 8.9 and 9.2 (two doublets, lH).
(b) Preparation of 3-chlorobenzoylamino(methylthio)-acetonitrile (Compound No.40) The foregoing amide (0.67 g) and 2 equivalents of p-toluenesulphonyl chloride in pyridine (10 ml) were kept atroom temperature for 48 hrs. The mixture was then poured into water (100 ml). The solid which separated was dried, and crystallised from chloroform-light petroleum to give the product (0.1 g), m.p. 115-117.
Found: C, 48.99; H, 3~71; N, 11.01 CloHgClN2OS
requires : C, 49.9; H, 3.77; N, 11.64~
5 (C~C13): 2.35 (s, 3H), 6.05 (d, lH~, 7.8-7.2 (m, 5H).
This Example illustrates the preparation of compound no 158 of Table 1 by the process of Scheme C.
(a) Preparation of Acetylamino(3,5-dimethylbenzoylamino) acetamide To a suspension of 3,5-dimethylbenzoylaminoacetonitrile (1 g) in glacial a~etic acid (20 ml) was added all at once bromine (0.85 g). After stirring the mixture at room temperature for 15 min. the white solid was separated, washed with anhydrous ether and then re-suspended in glacial acetic acid (10 ml). To this was added concentrated sulphuric acid (1.5 ml) and acetonitrile (8 ml). After 1 hour the mixture was poured intG water (30 ml) and extracted with chloroform (2 x 30 ml). The dried (MgS043 extract was evaporated and the residue crystallised frc)m aqueous ethanol to give the product (Q.38 g) as a white solid (Compound No 154 of Table I), 20 m.p. 244-5 Q .
Found: C, 58.49, H, 6.42; M, 15.46 C13H17N3O3 requires : C, 59.13: H, 6.46; M, 15.g7%
~ (DMSO-d6): 1.9 (3H,s), 2.3 (6H,s), 5.8 (lH,dd), C2.
7.1-7.5 (5H,m), 8.3 (lH,d), 8.7 (lH,d).
(b) Preparation of Acetylamino (3,5-dime~hylbenzoylamino) .
acetonltrile The foregoing acetamide ( 1. O c ) w2s dissolved in anhydrous ~8 pyridine (25 ml) which was then cooled to -25.
Trifluoroacetic anhydride ~1.5 g) was added dropwise to the cooled and stirred solution, and following the addition the solution was allowed to come to 0 whereupon it was poured into water (70 ml) and extracted with ether (2 x 50 ml). Evaporation of the ethereal extracts and crystallisation of the residue from ethyl acetate-hexane gave the product (0.6 g) as a pale cream solid, mOp. 195-7o.
Found: C, 62.51; H, 5.98; N, 17.16 C13H15N302 requires : C, 63.67; H, 6.12; N, 17.14%
~ (DMS0-d6) : 1.8 ~3H,s), 2.2 (6H,s), 6.2 (lH,dd~, 7.1 (l~,s), 7.4 (2H,s), 9.1 (lH,s), 9.5 (lH,s).
EXAMPL~ 6 This Example illustrates the preparation of compound no.153 of Table I by ',he process of Scheme D.
(a) Preparation of Methyl Acetylamino (3,5-dichlorobenzoylamino) acetate .
A mixture of 3,5-dichlorobenzamide (19.0 g) and methyl glyoxylate (8.8 g) in ethyl acetate (300 ml) was heated under reflux for 8 hours. The solvent was removed and the residual adduct was crystallised from chloroform-light petroleum. A portion (4.0 g) of the adduct was dissolved in a mixture of glacial acetic acid (30 ml) and acetonitrile (10 ml) with stirring, and then concentrated sulphuric acid (4 ml) was added. The mixture was kept at room temperature overnight when water (100 ml) was added.
The precipitated solid was washed with water, dried, and crystallised 'rom ethanol to give the product (2.45 g) as a colourless crystalline solid, m.p. 235-237.
3 ~ L~
Found: C, 45.24; Il, 3-88, N, 8.84 C12H12C12N2O4 requires : C, 45.14; H, 3-76, N, 8.77~
S(~MSO-d6) : 1.95 13H,s), 3.7 (3H,s), 5-9 (lH,dd) t 7-95 (3H,m), 8.9 (lH,d), 9~75 (lH,d).
(b) Preparation of Acetvlamino (3,5~dichlorobenzoylamino) acetamide The foregoing ester (1.46 g~ was dissolved in dimethylformamide (70 ml) which was then saturated with ammonia (gas) and the mixture kept for 7 days. The solvent was removed under reduced pressure and the residue crystallised from aqueous dimethylformamide to give the product (0~72 g), m.p. 267-268 (dec).
Found: C, 43.62; H, 3.72; N, 13.82 CllHllC12N303 requires : C, 43.42, H, 3.62; N, 13.82%
~ (~MSO-d6): 1.95 (3H,s), 5.9 (lH,dd), 7.3 (2H,d,broad) 7.6 (lH,m), 7.9 (2H,m), 8.35 (lH,d), 9.2 (lH,d).
(c) Preparation of Acetylamino (3,5-dichloroben~ovlamino) acetonitrile _ The foregoing acetamide (0.5 g~ in anhydrous pyridine (10 ml) at -25 was treated with trifluoroacetic anhydride as described above. The product (0~18 g), crystallised from aqueous dimethylformamide, had m.p. 227-228.
Found: C~ 45.95; H, 3.12; N, 14.43 Cl1HgC12N3O2 reauires : C, 46.15; H, 3.15; N, 14.68%
,~ ISO-d6): 1.95 (3H,s), 6.4 (lH,dd), 7.9 (3H,m), 9.35 (lH,d), 10.0 (lH,d).
5 (~ p ~ r~
EXA~PLE 7 This Example illustrates the preparation of compound no.159 of Table I bv the process of Scheme E.
(a) N-Furfuryl-3,5-dichlorobenæamide To a vigorously stirred solution of furfurylamine ~2.78 g) in ethyl acetate (40 ml) was added sodium hydroxide (1.15 g) in water (45 ml), followed immediately by the addition of a solution of 3,5-dichlorobenzoyl chloride (6.0 g) in ethyl acetate (20 ml). Following the mild exothermic reaction the ethyl acetate layer was removed, dried (MgS04), and evaporated. Crystallisation of the residue from cyclohexane gave the product ~6.6 g) as colourless needles.
(b) Preparation of N-Furfurvl-3,5-dichlorobenzoylamino ~ , . , _ _ (methoxy) acetonitrile To a stirred suspension of sodium hydride (0.58 g) in anhydrous tetrahydrofuran (40 ml) was added in portions the foregoing a~ide (3.0 g). Following the addition and cessation of hydrogen evolution was added with stirring methyl 2-bromo-2-methoxy acetate (2.04 g) and the mixture stirred for a further 2 hours at room temperature. Water (100 ml) was then acded and the solution extracted with methylene chloride (3 x 50 ml) and the extracts dried and evaporated. The resultant crude oily ester was dissolved in methanol (20 ml) which was then saturated with ammonia gas and kept overnight. The solvent was removed under reduced pressure and the residual oil triturated with ether to give crude amide (1.91 g). The crude amide (1.75 g) was dissolved in anhvdrous pyridine (10 ml), cooled to 51 1~3~3~4 0~ with stirring and phosphorus oxychloride ~0.84 g) added dropwise so that the temperature of the mixture did not exceed 0. After 25 minu~es at 0, water (100 ml) was added and the mixture was extracted with ether (40 ml).
The dried (MgS04) ether extract was chromatographed on silica using diisopropyl ether as the eluent. Following elution from the column and evaporation of th~ solvent the product (1.24 g) was obtained as a colourless oil which slowly crystallised, m.p. 89-90.
~ (CDC13): 3.4 (3H,s), 4.65 (2H,s), 6.1 (lH,s,broad)
6.3 (2H,m), 7.3-7.5 (4H,m).
~XAMPLE 8 This ~xample illustrates the preparation of compound no.142 of Table I by the process of Scheme F.
Preparation of N-Benzyl-3,5-dimethylbenzoylamino(methoxy) acetonitrile To a stirred solution of glycollonitrile (25 g) in methanol was added dropwise over 45 minutes benzylamine (46.9 g) keeping the temperature of the reaction between 15-20. Following the addition the reaction mixture was kept overnight at room temperature, and then distilled to give benzylaminoacetonitrile (42.0 g) as a colourless oil, b.p. 120/15 mm. Reaction of this (3.0 g) with 3,5-dimethylbenzoyl chloride (3.46 g) as described above gave crude N-benzyl-3,5-dimethylbenzovlaminoacetonitrile (5.81 g) as a colourless viscous oil which was used in the next staae without further purification. To this crude amide (2.0 g) in anhydrous methylene chloride (8 ml) was added sulphuryl chloride (0.97 g). ~ollowing the cessation of gas evolution (ca. 15 min.), anhyc-ous methanol (20 ml) and finely powdered anhydrouc; potassi~l carborlate (1.95 g) was added to ~he mixture which was then stirred for 30 minutes. Solids were removed from the solu-~ion which was then evaporated and the residual oil chromatoaraphed on a column of silica using methylene chloride as an eluent.
Following elution from the column and evaporation of the solvent, the product (1.2 g) was obtained as a very pale-yellow viscous oil.
Found~ C, 73.87, H, 6.67~ N, 9.22 ClgH20N202 requires : C, 74~Q2; H, 6.49, N, 9.09~
(CDC13j: 2~28 (6H,s), 3.25 [3H,s), 4.75 (2H,s), 5.85 (lH,s,broad), ca. 7.0-7.4 ~8H,m).
This E~ample illustrates the preparation of compound no.
84 of Table I ~y the process of Scheme C-.
Preparation of 3-chlorobenzovlamino(ethoxy)thioacetamide Into a solution of 3- chlorobenzoylamino(ethoxy) acetonitrile (1 g) in toluene (50 ml) containing triethylamine (1 g) was passed hvdrogen sulphide gas. ~he precipitated product (0.72 g) was collected and crystallised from chloroform-light petroleum. m.p. 136-137.
Found: C, 48.53; H, 4.8a; N, 10.19 CllHl~C1N202S
requires : C, 48.44; H, 4.80; N, 10.27%.
3 ~
EXA~PLE lO
This Example illustrates the herbicidal properties of compounds of Table I. The compounds were submitted to herbicide tests as described below.
~ach compound was formulated for test by mixing an appropriate amount of it with 5 ml of an emulsion prepared by diluting 160 ml of a solution containing 21.8 grams per litre of Span 80 and 78.2 grams per litre of Tween 20 in methylcyclohexanone to 500 ml with water. Span 80 is a Trade Mark for a surface-active agent comprising sorbitan monolaurate. Tween 20 is a Trade Mark for a surface-active agent comprisina 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 44 ml with water. The spray composition so prepared was sprayed on to youna pot plants (post-emergence test) of the species named in Tables 2 and 3 below, at a rate equivalent to lO00 litres er hectare.
~amaqe to plants was assessed 13 days after spraying by comparison with untreated plants, on a scale of 0 to 5 where 0 is 0 to 20% damage and 5 is complete kill. In the table of results, a dash (-) means 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 lO00 litres per hectare. The seeds were then covered with further soil. 20 days after spraying, the seedlings in the sprayed fibre trays were compared with the seedlings in unsprayed control trays, the damage being assessed on the sarne scale Of 0 to 5-The results of the tests are given in Tables 2 and 3 below.
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~XAMPLE 8 This ~xample illustrates the preparation of compound no.142 of Table I by the process of Scheme F.
Preparation of N-Benzyl-3,5-dimethylbenzoylamino(methoxy) acetonitrile To a stirred solution of glycollonitrile (25 g) in methanol was added dropwise over 45 minutes benzylamine (46.9 g) keeping the temperature of the reaction between 15-20. Following the addition the reaction mixture was kept overnight at room temperature, and then distilled to give benzylaminoacetonitrile (42.0 g) as a colourless oil, b.p. 120/15 mm. Reaction of this (3.0 g) with 3,5-dimethylbenzoyl chloride (3.46 g) as described above gave crude N-benzyl-3,5-dimethylbenzovlaminoacetonitrile (5.81 g) as a colourless viscous oil which was used in the next staae without further purification. To this crude amide (2.0 g) in anhydrous methylene chloride (8 ml) was added sulphuryl chloride (0.97 g). ~ollowing the cessation of gas evolution (ca. 15 min.), anhyc-ous methanol (20 ml) and finely powdered anhydrouc; potassi~l carborlate (1.95 g) was added to ~he mixture which was then stirred for 30 minutes. Solids were removed from the solu-~ion which was then evaporated and the residual oil chromatoaraphed on a column of silica using methylene chloride as an eluent.
Following elution from the column and evaporation of the solvent, the product (1.2 g) was obtained as a very pale-yellow viscous oil.
Found~ C, 73.87, H, 6.67~ N, 9.22 ClgH20N202 requires : C, 74~Q2; H, 6.49, N, 9.09~
(CDC13j: 2~28 (6H,s), 3.25 [3H,s), 4.75 (2H,s), 5.85 (lH,s,broad), ca. 7.0-7.4 ~8H,m).
This E~ample illustrates the preparation of compound no.
84 of Table I ~y the process of Scheme C-.
Preparation of 3-chlorobenzovlamino(ethoxy)thioacetamide Into a solution of 3- chlorobenzoylamino(ethoxy) acetonitrile (1 g) in toluene (50 ml) containing triethylamine (1 g) was passed hvdrogen sulphide gas. ~he precipitated product (0.72 g) was collected and crystallised from chloroform-light petroleum. m.p. 136-137.
Found: C, 48.53; H, 4.8a; N, 10.19 CllHl~C1N202S
requires : C, 48.44; H, 4.80; N, 10.27%.
3 ~
EXA~PLE lO
This Example illustrates the herbicidal properties of compounds of Table I. The compounds were submitted to herbicide tests as described below.
~ach compound was formulated for test by mixing an appropriate amount of it with 5 ml of an emulsion prepared by diluting 160 ml of a solution containing 21.8 grams per litre of Span 80 and 78.2 grams per litre of Tween 20 in methylcyclohexanone to 500 ml with water. Span 80 is a Trade Mark for a surface-active agent comprising sorbitan monolaurate. Tween 20 is a Trade Mark for a surface-active agent comprisina 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 44 ml with water. The spray composition so prepared was sprayed on to youna pot plants (post-emergence test) of the species named in Tables 2 and 3 below, at a rate equivalent to lO00 litres er hectare.
~amaqe to plants was assessed 13 days after spraying by comparison with untreated plants, on a scale of 0 to 5 where 0 is 0 to 20% damage and 5 is complete kill. In the table of results, a dash (-) means 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 lO00 litres per hectare. The seeds were then covered with further soil. 20 days after spraying, the seedlings in the sprayed fibre trays were compared with the seedlings in unsprayed control trays, the damage being assessed on the sarne scale Of 0 to 5-The results of the tests are given in Tables 2 and 3 below.
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~-a~es of test plants in Ta~les 2 and 3 _ __ ___ Sb Suga.r beet ~ Rape Ct Cotton 5 Sy Soya Bean Mz Maize ~w llinter wheat Rc Rice Sn Senecio vulgaris 10 Ip Ipomoea purpurea Am A~aranthus retroflexus Pi Polygonum aviculare Ca Chenopodium album -Po Portulaca oleracea Xs and Xa Xanthiu~ spinosum -Ab Abutilon theophrastii Cv Convolvulus arvensis Ot/Av Oats tcultivated in pre-emergence test and Avena fatua (wild oats) in post-emergence test~ (Applies to Table 2; in Table 3 only Avena fatua is used) __ Dg Digitaria sanguinalis Pu Poa annua -St Setaria viridis 25 Ec Echinochloa crus-galli Sh Sorghum halepense Ag Agropyron repens Cn Cyperus rotund~s Ga Galium aparine 30 Co Cassia obtusifolia Al Alopecurus myosuroides
7 I
".X~E~L,E ll This Exa~ple further illustra-tes the herbicid21 proper-ties of compo~lnds according to the in~ention. Tests were carried out as clescriDed in Example 10, but using different ranges of test plants. The pos.-emergence test was slightly different from the one described in Exa~ple 10 in tha~ the seeds were sown in trays of soil and covered with a few millimetres of soil before spraying the test compound, whereas in the previous test the seeds were sprayed directlyO
The compounds were formulated in a similar way to that described in Example 10, but usina cyclohexanone solution containing Synperonic NPE 1800*(a nonyl-phenol-propylene oxide - ethylene oxide condensate~ and Tween 85*
~a condensate of sorbitan tri-oleate with 20 molar ~roportions of ethylene oxide~ instead of the methylcyclohexanone solution of suxfac-tants described in that Exa~ple. Tne da~age to the test plants was assessed on a scale of 0 to 9 where 0 represents 0 to 10~ damase to the plant and 9 is 90 to 100% damage. Assessments were made 26 days after spraying the compounds. I~e results are given in Tables 4 and 5 below. ~
"--, ., , ,,_ * Reg. 'l~rade Marks -~ --- - -----U~ ~D I ~ V
~:
G~ I` a~ o~
a~ ~* G~
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t~ ~ u~ c3 G~
~ ~ ~ ~ C~
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_ O
H
~ U S ~ _l ~ ~ ~ ~ ~ ~ ~ ~ d~
~IX O ooooo ooooo '_ . _ O O I ct~ ~
~ I ._. _ I
The na~es o~ the test plants in Table 4 ~-lw ~inter wheat Br Barley Pe Peas 5 ~p Rape Sb Sugar beet Lt Lettuce Av Avena fatua Al Alopecurus myosuroides 10 Bt Bromus tectoru~
Ag Agropyron repens Ga Galium aparine S~ Stellaria edia Ca Chenopodium album 15 Pi Polygonum viculare Ma Matricaria inodora Sp Sinapis alba /~' ~. ~
~ /
__ ~ _ __ _ C~ o o o o o ~ l l ~ U~
&'~ ~ ~ ~ o ~ ~ ~`
~ _. ~ o o E~ X o ~ o ~ o ~ ~ ~ ~ ~ U~
~ 'u~ ~ ~ ~ ,1 ~n ~ u~ ~ s~ c~
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E~ u:~ u~ ~ ~1 .
C~ C`J C`~ ~ ~
V ~ ~ ~ ~
~r: r- o~ ~ ~ r ~: a~ r- o ~
,t o o o D~ _ 3 __ G Z 1~ _ ~ O N
3~
The names of test ~lants in Table_5 .
Mz Maize Rc Rice Sy Soya bean Ct Cotton To Tomato Sg Sorghum Eh Euphorbia heterophylla Ip Ipomoea purpurea 10 Ab Abutilon theophrasti Se Sesbania xaltata Si Sida spinosa Ds Datura stramonium Xa Xanthium pensylvanicum 15 Ec Echinochloa crus-galli Dg Digitaria sanguinalis St Setaria viridis Sh Sorghum hale~ense Pm Panicum maximum 20 Cd Cyperus difformis Cn Cyperus rotunius , , .
~f~
EXAMPI.E 12 This Example ill~strates a composltion according to the invention w~ich comprises an e~ulsifiable concentrate.
The following ingredients were thoroushly mixed to give a solution.
Compound No. 2 of Table I10%
Ethylene dichloride 40 Calcium dodecylbenzenesulphate 5~
"Lubrol" L 10%
"Aromasol" H 35%
EXP~PLE 13 A composition in the form of grains readily dispersible in a liquid, e.g. water, was prepared by grinding together the first three ingredients in the presence of added water and then mixing in the sodiu~
acetate. The resultant mixture ~as dried and passed through a British Standard r,~esh sieve, size 44-100, to obtain the desired size of grains.
Compound Mo. 4 of Table I 50 "Dispersol" T 25~
"Lubrol" APN 5 1.5%
Sodium acetate 23.5 The following ingredients were ground together to produce a powder formulation readily dispersi~le in liquids.
;:L~ 2~
CO~pour~ o. ~ of r~ T ~5Q
"Dispersol" T 5~, "L.issapol" NX * 0-5%
"Cellofas" B600 2 Sodium acetate 47.5%
~ he active ingredient was dissolved in acetone and the resultant liquid was sprayed on to the granules of china clay, The solvent was then allowed to evaporate to produce a granular composi~ion.
Compound No.18 of Table I 5%
China clay granules 95 A composition suitable for use as a seed dressing was prepared by mi~ing the following three ingredients.
Compound No.2 of Table I 50%
Mineral oil ~%
China clay 48%
E~1PLE 17 A dusting powder was prepared by mi~ing the active ingredient with -talc.
Compound No. ~ of Table I 5 Talc 95 * Reg. Trade Mark ~8 ~. R,~
~ Pr-r~ l~
A CoL formulation was prepared by b.~ r~illinc3 the constituents set out below and then for~ing an aqueous suspension OL the ground mixture with ~Jater.
Compound No. 8 of Table I 40%
"Dispersol" T 10%
"Lubrol" APN5 1~
Water 49%
A dispersible powder for~ulation was made by mixing tosether the ingredients set out below and then grinding the r~ix,ure until all were thoroughly mixed.
Co~pound No. 18 of Table I 25%
"Aerosol" OT/B* 2 "Dispersol" A~C. 5 China clay 28 Silica 40Q
This Example illustrates the prepara-tiorl of a dispersible po~der formulation. The ingredients ~ere ~ixed and the mixture then ground in a comminution ~till.
Cor~pound No.20 of Table I 25 "PER~IINAL" BX* 1 "Dispersol" T 5~
Polyvinylpyrrolidone 10%
Silica 25~
C~ina clay 34%
* Re~. Trade Marks 7'3 F.,~MPL,E 21 The ingredients set out below were formulated into a dispers~ble powcler by mixing then grinding the i.ngredierlts .
Compound ~o. 2 of Table 1 25 "Aerosol" OT/B 2 "Dispersol" A* 5 China clay 68~
In Examples 1 to 10 the proportions of the ingredients given are by weight and the Examples were all repeated using, as active ingredient, the other compounds of Table I.
There now follows an explanation of the composi.ions or substances represented by the various Trade MarXs and l'rade Names mentioned above.
15 L~BROL L : a condensate of nonyl phenol (1 mole) with ethylene oxide (1~ moles).
AROMASOL H : a solvent mi~ture of alkyl-benzenes 20 DISPERSOL. T ~ND AC : a mixture of socium sul~hate and a condensate of formalde-hyde with sodium naphthalene sul~honate L~BROL APN 5 : a condensate o~ nonyl phenol ~5 (1 mole) with ethvlene oxide (5.5 moles~
* Reg. Trade Mark
".X~E~L,E ll This Exa~ple further illustra-tes the herbicid21 proper-ties of compo~lnds according to the in~ention. Tests were carried out as clescriDed in Example 10, but using different ranges of test plants. The pos.-emergence test was slightly different from the one described in Exa~ple 10 in tha~ the seeds were sown in trays of soil and covered with a few millimetres of soil before spraying the test compound, whereas in the previous test the seeds were sprayed directlyO
The compounds were formulated in a similar way to that described in Example 10, but usina cyclohexanone solution containing Synperonic NPE 1800*(a nonyl-phenol-propylene oxide - ethylene oxide condensate~ and Tween 85*
~a condensate of sorbitan tri-oleate with 20 molar ~roportions of ethylene oxide~ instead of the methylcyclohexanone solution of suxfac-tants described in that Exa~ple. Tne da~age to the test plants was assessed on a scale of 0 to 9 where 0 represents 0 to 10~ damase to the plant and 9 is 90 to 100% damage. Assessments were made 26 days after spraying the compounds. I~e results are given in Tables 4 and 5 below. ~
"--, ., , ,,_ * Reg. 'l~rade Marks -~ --- - -----U~ ~D I ~ V
~:
G~ I` a~ o~
a~ ~* G~
E ~ r-- G\ ~ ~ r~ I~ c~
t~ ~ u~ c3 G~
~ ~ ~ ~ C~
P a~ ~ o ~ ~ o c~
E~ ~ ~ ~ ~ `D
~c~ ~ a~
~- o o U~ o o o ,t ~ o o o u~ a:~ ~ ~ u~ ~ O
P~ CO o o r~ o O o o ~ o O
):4 ~ ~ O t`~ O O t~ O O O ~
~¢ a~ 1` t` ~ G~
P 3 ~ ~ s\c\ r~
~ Z .
H
~:
~ 0 u~ ~ ~ a) a~ ~n Ln 1~ h 0 h h O O O h h 0 O O
~ 1 ~ ~ G C~ ~ ~ ~ ~ a~ ~ ~ ~ D~
P ~
_ O
H
~ U S ~ _l ~ ~ ~ ~ ~ ~ ~ ~ d~
~IX O ooooo ooooo '_ . _ O O I ct~ ~
~ I ._. _ I
The na~es o~ the test plants in Table 4 ~-lw ~inter wheat Br Barley Pe Peas 5 ~p Rape Sb Sugar beet Lt Lettuce Av Avena fatua Al Alopecurus myosuroides 10 Bt Bromus tectoru~
Ag Agropyron repens Ga Galium aparine S~ Stellaria edia Ca Chenopodium album 15 Pi Polygonum viculare Ma Matricaria inodora Sp Sinapis alba /~' ~. ~
~ /
__ ~ _ __ _ C~ o o o o o ~ l l ~ U~
&'~ ~ ~ ~ o ~ ~ ~`
~ _. ~ o o E~ X o ~ o ~ o ~ ~ ~ ~ ~ U~
~ 'u~ ~ ~ ~ ,1 ~n ~ u~ ~ s~ c~
E~ ,.~0~ ~ ~ _~ ~ v .c ~ ~ ~ U~
E~ u:~ u~ ~ ~1 .
C~ C`J C`~ ~ ~
V ~ ~ ~ ~
~r: r- o~ ~ ~ r ~: a~ r- o ~
,t o o o D~ _ 3 __ G Z 1~ _ ~ O N
3~
The names of test ~lants in Table_5 .
Mz Maize Rc Rice Sy Soya bean Ct Cotton To Tomato Sg Sorghum Eh Euphorbia heterophylla Ip Ipomoea purpurea 10 Ab Abutilon theophrasti Se Sesbania xaltata Si Sida spinosa Ds Datura stramonium Xa Xanthium pensylvanicum 15 Ec Echinochloa crus-galli Dg Digitaria sanguinalis St Setaria viridis Sh Sorghum hale~ense Pm Panicum maximum 20 Cd Cyperus difformis Cn Cyperus rotunius , , .
~f~
EXAMPI.E 12 This Example ill~strates a composltion according to the invention w~ich comprises an e~ulsifiable concentrate.
The following ingredients were thoroushly mixed to give a solution.
Compound No. 2 of Table I10%
Ethylene dichloride 40 Calcium dodecylbenzenesulphate 5~
"Lubrol" L 10%
"Aromasol" H 35%
EXP~PLE 13 A composition in the form of grains readily dispersible in a liquid, e.g. water, was prepared by grinding together the first three ingredients in the presence of added water and then mixing in the sodiu~
acetate. The resultant mixture ~as dried and passed through a British Standard r,~esh sieve, size 44-100, to obtain the desired size of grains.
Compound Mo. 4 of Table I 50 "Dispersol" T 25~
"Lubrol" APN 5 1.5%
Sodium acetate 23.5 The following ingredients were ground together to produce a powder formulation readily dispersi~le in liquids.
;:L~ 2~
CO~pour~ o. ~ of r~ T ~5Q
"Dispersol" T 5~, "L.issapol" NX * 0-5%
"Cellofas" B600 2 Sodium acetate 47.5%
~ he active ingredient was dissolved in acetone and the resultant liquid was sprayed on to the granules of china clay, The solvent was then allowed to evaporate to produce a granular composi~ion.
Compound No.18 of Table I 5%
China clay granules 95 A composition suitable for use as a seed dressing was prepared by mi~ing the following three ingredients.
Compound No.2 of Table I 50%
Mineral oil ~%
China clay 48%
E~1PLE 17 A dusting powder was prepared by mi~ing the active ingredient with -talc.
Compound No. ~ of Table I 5 Talc 95 * Reg. Trade Mark ~8 ~. R,~
~ Pr-r~ l~
A CoL formulation was prepared by b.~ r~illinc3 the constituents set out below and then for~ing an aqueous suspension OL the ground mixture with ~Jater.
Compound No. 8 of Table I 40%
"Dispersol" T 10%
"Lubrol" APN5 1~
Water 49%
A dispersible powder for~ulation was made by mixing tosether the ingredients set out below and then grinding the r~ix,ure until all were thoroughly mixed.
Co~pound No. 18 of Table I 25%
"Aerosol" OT/B* 2 "Dispersol" A~C. 5 China clay 28 Silica 40Q
This Example illustrates the prepara-tiorl of a dispersible po~der formulation. The ingredients ~ere ~ixed and the mixture then ground in a comminution ~till.
Cor~pound No.20 of Table I 25 "PER~IINAL" BX* 1 "Dispersol" T 5~
Polyvinylpyrrolidone 10%
Silica 25~
C~ina clay 34%
* Re~. Trade Marks 7'3 F.,~MPL,E 21 The ingredients set out below were formulated into a dispers~ble powcler by mixing then grinding the i.ngredierlts .
Compound ~o. 2 of Table 1 25 "Aerosol" OT/B 2 "Dispersol" A* 5 China clay 68~
In Examples 1 to 10 the proportions of the ingredients given are by weight and the Examples were all repeated using, as active ingredient, the other compounds of Table I.
There now follows an explanation of the composi.ions or substances represented by the various Trade MarXs and l'rade Names mentioned above.
15 L~BROL L : a condensate of nonyl phenol (1 mole) with ethylene oxide (1~ moles).
AROMASOL H : a solvent mi~ture of alkyl-benzenes 20 DISPERSOL. T ~ND AC : a mixture of socium sul~hate and a condensate of formalde-hyde with sodium naphthalene sul~honate L~BROL APN 5 : a condensate o~ nonyl phenol ~5 (1 mole) with ethvlene oxide (5.5 moles~
* Reg. Trade Mark
8~
CELLOFAS B600 : a sodium carboxymethyl cellulose thickener.
The compounds were tested against a variety of foliar fungal diseases of plants. The techniques employed were as follows:
The plants were grown in John Innes Potting Compost (No.l or 2) in 4 cm diameter mini-pots. A layer of fine sand was placed at the bottom to facilitate uptake of test compound by the roots. The test compounds were formulated either by bead milling with aqueous ~ispersol T or as a solution in acetone or acetone/ethanol which was diluted to the required concentration immediately before use. For the foliage diseases suspensions (100 ppm active ingredient) were sprayed on to the foliage and applied to the roots of the same plant via the soil. Exceptions ~ere the tests on Plasmopara viticola _. .
and Venturia inaequalis in which the compound was sprayed .
on to the foliage only. Sprays were applied to maximum retention,and root drenches were applied to a final concentration equivalent to approximately 40 ppm a.i./dry soil. Tween 20, to give a final concentration of 0.05~ was added when the sprays were applied to cereals.
E`or most of the tests the compound was applied to the soil (roots) and to the foliage (by spraying) one or two days before the plant was inoculated with the dlseases.
An exception was the test on Erysiphe graminis in which the plants were inoculated 24 hours before treatment.
After inoculation, the plants were put into an appropriate environment to allow infection to take place and then incubated until the disease was ready for - assessment.
81 ~ r~
The period between inoculation and assessment varied fro~ four to fourteen days according to the disease and environment.
The disease control was recorded by the -following S grading:
4 = no disease 3 = trace - 5% of disease on untrea~ed plants 2 = 6-25~ of disease on untreated plants 1 = 26-59~ of disease on untreated plants 0 = 60-100% of disease on untreated plants The results are shown in Table 6 below.
In the table below the following compounds have been omitted for the reasons stated.
Compounds Nos. 5, 6, 7, 14, 16~ 21, 23, 25, 27, 29, 32, 40, 58, 88, 115, 123, 140 were not tested at the standard primary screen rate.
Compounds Nos. 135, 136, 138, 142-145, 147, 148 and 160 were not tested.
A dash, thus "-", in the table in any column indicates that the particular compound was not tested against that particular disease.
An asterisk, thus "*" against the disease srading in the column headed "BOTRYTIS CINEREA (TOMATO)" signifies that the test plant material used in this instance were grape l~erries. ~
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CELLOFAS B600 : a sodium carboxymethyl cellulose thickener.
The compounds were tested against a variety of foliar fungal diseases of plants. The techniques employed were as follows:
The plants were grown in John Innes Potting Compost (No.l or 2) in 4 cm diameter mini-pots. A layer of fine sand was placed at the bottom to facilitate uptake of test compound by the roots. The test compounds were formulated either by bead milling with aqueous ~ispersol T or as a solution in acetone or acetone/ethanol which was diluted to the required concentration immediately before use. For the foliage diseases suspensions (100 ppm active ingredient) were sprayed on to the foliage and applied to the roots of the same plant via the soil. Exceptions ~ere the tests on Plasmopara viticola _. .
and Venturia inaequalis in which the compound was sprayed .
on to the foliage only. Sprays were applied to maximum retention,and root drenches were applied to a final concentration equivalent to approximately 40 ppm a.i./dry soil. Tween 20, to give a final concentration of 0.05~ was added when the sprays were applied to cereals.
E`or most of the tests the compound was applied to the soil (roots) and to the foliage (by spraying) one or two days before the plant was inoculated with the dlseases.
An exception was the test on Erysiphe graminis in which the plants were inoculated 24 hours before treatment.
After inoculation, the plants were put into an appropriate environment to allow infection to take place and then incubated until the disease was ready for - assessment.
81 ~ r~
The period between inoculation and assessment varied fro~ four to fourteen days according to the disease and environment.
The disease control was recorded by the -following S grading:
4 = no disease 3 = trace - 5% of disease on untrea~ed plants 2 = 6-25~ of disease on untreated plants 1 = 26-59~ of disease on untreated plants 0 = 60-100% of disease on untreated plants The results are shown in Table 6 below.
In the table below the following compounds have been omitted for the reasons stated.
Compounds Nos. 5, 6, 7, 14, 16~ 21, 23, 25, 27, 29, 32, 40, 58, 88, 115, 123, 140 were not tested at the standard primary screen rate.
Compounds Nos. 135, 136, 138, 142-145, 147, 148 and 160 were not tested.
A dash, thus "-", in the table in any column indicates that the particular compound was not tested against that particular disease.
An asterisk, thus "*" against the disease srading in the column headed "BOTRYTIS CINEREA (TOMATO)" signifies that the test plant material used in this instance were grape l~erries. ~
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Claims (9)
1. Compounds of the formula wherein A is hydrogen, bromine or chlorine;
B is -CN where A is hydrogen and is -CONH2 where A is chlorine or bromine;
and wherein R1 is a C1-5 alkyl radical or a C3-5 alkenyl radical or a C1-5 alkyl or C3-5 alkenyl radical substituted with one or more substituents selected from C1-4 alkoxy, C1-4 alkylthio and halogen;
a phenyl or naphthyl radical or a phenyl or naphthyl radical substituted with one or more substituents selected from halogen, C1-4 alkoxy, methylenedioxy, ethylenedioxy, C1-4 alkyl, C1-4 haloalkyl, nitro and cyano;
a benzyl radical or benzyl radical substituted in the phenyl ring with one or more substitutents selected from halogen, C1-4 alkoxy, C1-4 alkylthio, nitro, cyano, C1-4 haloalkyl and C1-4 alkyl;
a furyl, benzfuryl, thienyl, pyridyl, thiazolyl or benzthiazolyl radical optionally substituted with one or more substituents selected from halogen, C1-4 alkoxy, methylenedioxy, ethylenedioxy, C1-4 alkyl, C1-4 alkylthio, C1-4 haloalkyl, nitro and cyano; or a heterocyclylmethyl radical in which the heterocyclyl radical is a furyl, benzfuryl, thienyl, pyridyl, thiazolyl or benzthiazolyl radical optionally substituted with one or more substituents selected from halogen, C1-4 alkoxy, methylenedioxy, ethylenedioxy, C1-4 alkyl, C1-4 alkylthio, C1-4 haloalkyl, nitro and cyano.
B is -CN where A is hydrogen and is -CONH2 where A is chlorine or bromine;
and wherein R1 is a C1-5 alkyl radical or a C3-5 alkenyl radical or a C1-5 alkyl or C3-5 alkenyl radical substituted with one or more substituents selected from C1-4 alkoxy, C1-4 alkylthio and halogen;
a phenyl or naphthyl radical or a phenyl or naphthyl radical substituted with one or more substituents selected from halogen, C1-4 alkoxy, methylenedioxy, ethylenedioxy, C1-4 alkyl, C1-4 haloalkyl, nitro and cyano;
a benzyl radical or benzyl radical substituted in the phenyl ring with one or more substitutents selected from halogen, C1-4 alkoxy, C1-4 alkylthio, nitro, cyano, C1-4 haloalkyl and C1-4 alkyl;
a furyl, benzfuryl, thienyl, pyridyl, thiazolyl or benzthiazolyl radical optionally substituted with one or more substituents selected from halogen, C1-4 alkoxy, methylenedioxy, ethylenedioxy, C1-4 alkyl, C1-4 alkylthio, C1-4 haloalkyl, nitro and cyano; or a heterocyclylmethyl radical in which the heterocyclyl radical is a furyl, benzfuryl, thienyl, pyridyl, thiazolyl or benzthiazolyl radical optionally substituted with one or more substituents selected from halogen, C1-4 alkoxy, methylenedioxy, ethylenedioxy, C1-4 alkyl, C1-4 alkylthio, C1-4 haloalkyl, nitro and cyano.
2. A compound of the formula wherein R1 is phenyl optionally substituted at any of the 3-, 4- or 5- positions with an alkyl, alkoxy or methylenedioxy group or with halogen.
3. A compound as claimed in Claim 2 wherein R1 is furyl, benzfuryl, thienyl, pryidyl, thiazolyl or benzthiazolyl.
4. A compound as claimed in Claim 2 wherein R1 is 3,4-methylenedioxy phenyl.
5. A compound as claimed in Claim 2 wherein R1 is 3,4-dichlorophenyl.
6. A compound of the formula R1 - CO - NH - ?H - CO - NH2 wherein R1 is phenyl optionally substituted at any of the 3-, 4- or 5- positions with an alkyl, alkoxy or methylenedioxy group or with halogen.
7. A compound as claimed in Claim 6 wherein R1 is furyl, benzfuryl, thienyl, pyridyl, thiazolyl or benzthiazolyl.
8. A compound as claimed in Claim 6 wherein R1 is 3,4-methylenedioxyphenyl.
9. A compound as claimed in Claim 6 wherein R1 is 3,4-dichlorophenyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000523062A CA1233824A (en) | 1981-03-04 | 1986-11-14 | Biologically active amide derivatives |
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8106817 | 1981-03-04 | ||
| GB8106817 | 1981-03-04 | ||
| GB8114393 | 1981-05-12 | ||
| GB8114393 | 1981-05-12 | ||
| CA000397435A CA1228366A (en) | 1981-03-04 | 1982-03-02 | Biologically active amide derivatives |
| CA000523062A CA1233824A (en) | 1981-03-04 | 1986-11-14 | Biologically active amide derivatives |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000397435A Division CA1228366A (en) | 1981-03-04 | 1982-03-02 | Biologically active amide derivatives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1233824A true CA1233824A (en) | 1988-03-08 |
Family
ID=27167210
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000523062A Expired CA1233824A (en) | 1981-03-04 | 1986-11-14 | Biologically active amide derivatives |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1233824A (en) |
-
1986
- 1986-11-14 CA CA000523062A patent/CA1233824A/en not_active Expired
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