Compounds and compositions

The invention concerns novel compounds of the formula I ##STR1## wherein: X is selected from halogen, nitro, cyano, alkyl, substituted alkyl, hydroxy, alkoxy, substituted alkoxy, alkenyl, alkynyl, alkenyloxy, alkynyloxy, acyloxy, alkoxycarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl, sulfamoyl, substituted sulfamoyl, amino, substituted amino, and the groups formyl and alkanoyl and the oxime, imine and Schiff base derivatives thereof; PA1 R.sup.1 is selected from hydrogen, alkyl, alkenyl, alkynyl, substituted alkyl, alkylsulfonyl, arylsulfonyl, acyl and an inorganic or organic cation; PA1 R.sup.2 is selected from alkyl, substituted alkyl, alkenyl, haloalkenyl, alkynyl and haloalkynyl; PA1 R.sup.3 is selected from alkyl, fluoroalkyl, alkenyl, alkynyl, and phenyl; PA1 m is an integer chosen from 3 to 5. The compounds of the invention show herbicidal properties and plant growth regulating properties and in further embodiments the invention provides processes for the preparation of compounds of formula I, intermediates useful in the preparation of the compounds of formula I, compositions containing as active ingredient a compound of formula I, and herbicidal and plant growth regulating processes utilizing compounds of formula I.

This invention relates to organic compounds having biological activity and 
in particular to organic compounds having herbicidal properties and plant 
growth regulating properties, to processes for the preparation of such 
compounds, to intermediates useful in the preparation of such compounds 
and to herbicidal compositions and processes utilizing such compounds and 
to plant growth regulating compositions and processes utilizing such 
compounds. 
The use of certain cyclohexane-1,3-dione derivatives as grass herbicides is 
known in the art. For example, the "Pesticide Manual" (C R Worthing 
Editor, The British Crop Protection Council, 6th Edition 1979) describes 
the cyclohexane-1,3-dione derivative known commercially as 
alloxydim-sodium (methyl 
3-[1-(allyloxyimino)butyl]-4-hydroxy-6,6-dimethyl-2-oxocyclohex-3-ene 
carboxylate) and its use as a grass herbicide. This compound is disclosed 
in Australian Patent No. 464 655 and its equivalents such as UK Patent No. 
1 461 170 and U.S. Pat. No. 3,950,420. 
More recently, at the 1980 British Crop Protection Conference ("1980 
British Crop Protection Conference--Weeds, Proceedings Vol 1, Research 
Reports", pp 39 to 46, British Crop Protection Council, 1980), a new 
cyclohexane-1,3-dione grass herbicide code named NP 55 
(2-(N-ethoxybutrimidoyl)-5-(2-ethylthiopropyl)-3-hydroxy-2-cyclohexen-1-on 
e) was announced. This compound is disclosed in Australian Patent 
Application No. AU-Al-35,314/78 and its equivalents. 
It has now been found that a new group of cyclohexane-1,3-dione derivatives 
which have a 5-phenyl substituent which is in turn substituted with three 
or more substituents exhibit particularly useful herbicidal activity and 
plant growth regulating activity. 
Accordingly the invention provides a compound of formula I: 
##STR2## 
wherein: X, which may be the same or different, are selected from the 
group consisting of: halogen; nitro; cyano; C.sub.1 to C.sub.6 alkyl; 
C.sub.1 to C.sub.6 alkyl substituted with a substituent selected from the 
group consisting of halogen, nitro, hydroxy, C.sub.1 to C.sub.6 alkoxy and 
C.sub.1 to C.sub.6 alkylthio; C.sub.2 to C.sub.6 alkenyl; C.sub.2 to 
C.sub.6 alkynyl; hydroxy; C.sub.1 to C.sub.6 alkoxy; C.sub.1 to C.sub.6 
alkoxy substituted with a substituent selected from halogen and C.sub.1 to 
C.sub.6 alkoxy; C.sub.2 to C.sub.6 alkenyloxy; C.sub.2 to C.sub.6 
alkynyloxy; C.sub.2 to C.sub.6 alkanoyloxy; (C.sub.1 to C.sub.6 
alkoxy)carbonyl; C.sub.1 to C.sub.6 alkylthio; C.sub.1 to C.sub.6 
alkylsulfinyl; C.sub.1 to C.sub.6 alkylsulfonyl; sulfamoyl; N-(C.sub.1 to 
C.sub.6 alkyl)sulfamoyl; N,N-di(C.sub.1 to C.sub.6 alkyl)sulfamoyl; 
benzyloxy; substituted benzyloxy wherein the benzene ring is substituted 
with from one to three substituents selected from the group consisting of 
halogen, nitro, C.sub.1 to C.sub.6 alkyl, C.sub.1 to C.sub.6 alkoxy and 
C.sub.1 to C.sub.6 haloalkyl; the group NR.sup.8 R.sup.9 wherein R.sup.8 
and R.sup.9 are independently selected from the group consisting of 
hydrogen, C.sub.1 to C.sub.6 alkyl, C.sub.2 to C.sub.6 alkanoyl, benzoyl 
and benzyl; the groups formyl and C.sub.2 to C.sub.6 alkanoyl and the 
oxime, imine and Schiff base derivatives thereof; and at least one of X is 
not selected from the group consisting of halogen, C.sub.1 to C.sub.6 
alkyl and C.sub.1 to C.sub.6 alkoxy; 
R.sup.1 is selected from the group consisting of: hydrogen; C.sub.1 to 
C.sub.6 alkyl; C.sub.2 to C.sub.6 alkenyl; C.sub.2 to C.sub.6 alkynyl; 
substituted C.sub.1 to C.sub.6 alkyl wherein the alkyl group is 
substituted with a substituent selected from the group consisting of 
C.sub.1 to C.sub.6 alkoxy, C.sub.1 to C.sub.6 alkylthio, phenyl and 
substituted phenyl wherein the benzene ring is substituted with from one 
to three substituents selected from the group consisting of halogen, 
nitro, cyano, C.sub.1 to C.sub.6 alkyl, C.sub.1 to C.sub.6 haloalkyl, 
C.sub.1 to C.sub.6 alkoxy and C.sub.1 to C.sub.6 alkylthio; C.sub.1 to 
C.sub.6 (alkyl) sulfonyl; benzenesulfonyl; substituted benzenesulfonyl 
wherein the benzene ring is substituted with from one to three 
substituents selected from the group consisting of halogen, nitro, cyano, 
C.sub.1 to C.sub.6 alkyl, C.sub.1 to C.sub.6 haloalkyl, C.sub.1 to C.sub.6 
alkoxy and C.sub.1 to C.sub.6 alkylthio; and acyl group; and an inorganic 
or organic cation; 
R.sup.2 is selected from the group consisting of: C.sub.1 to C.sub.6 alkyl; 
C.sub.2 to C.sub.6 alkenyl; C.sub.2 to C.sub.6 haloalkenyl; C.sub.2 to 
C.sub.6 alkynyl; C.sub.2 to C.sub.6 haloalkynyl; substituted C.sub.1 to 
C.sub.6 alkyl wherein the alkyl group is substituted with a substituent 
selected from the group consisting of halogen, C.sub.1 to C.sub.6 alkoxy, 
C.sub.1 to C.sub.6 alkylthio, phenyl and substituted phenyl wherein the 
benzene ring is substituted with from one to three substituents selected 
from the group consisting of halogen, nitro, cyano, C.sub.1 to C.sub.6 
alkyl, C.sub.1 to C.sub.6 haloalkyl, C.sub.1 to C.sub.6 alkoxy and C.sub.1 
to C.sub.6 alkylthio; 
R.sup.3 is selected from the group consisting of: C.sub.1 to C.sub.6 alkyl; 
C.sub.1 to C.sub.6 fluoroalkyl; C.sub.2 to C.sub.6 alkenyl; C.sub.2 to 
C.sub.6 alkynyl; and phenyl; and 
m is an integer chosen from 3 to 5. 
When in the compound of formula I X is chosen from the groups formyl and 
C.sub.2 to C.sub.6 alkanoyl and the oxime, imine and Schiff base 
derivatives thereof, the nature of the oxime, imine and Schiff base 
derivatives is not narrowly critical. Although not intending to be bound 
by theory, it is believed that in the plant the (substituted) imine group 
may be removed to give the corresponding compound of formula I in which X 
is formyl or C.sub.2 to C.sub.6 alkanoyl. Suitable values for the groups 
formyl and C.sub.2 to C.sub.6 alkanoyl and the oxime, imine and Schiff 
base derivatives thereof include groups of the formula 
--C(R.sup.10).dbd.NR.sup.11 wherein R.sup.10 is chosen from hydrogen and 
C.sub.1 to C.sub.5 alkyl, and R.sup.11 is chosen from hydrogen, C.sub.1 to 
C.sub.6 alkyl, phenyl, benzyl, hydroxy, C.sub.1 to C.sub.6 alkoxy, phenoxy 
and benzyloxy. 
When in the compound of formula I R.sup.1 is chosen from acyl the nature of 
the acyl group is not narrowly critical. Although not intending to be 
bound by theory, it is believed that when R.sup.1 is acyl the acyl group 
is removed in the plant by hydrolysis to give the corresponding compound 
of formula I in which R.sup.1 is hydrogen. Suitable acyl groups include: 
alkanoyl, for example C.sub.2 to C.sub.6 alkanoyl; aroyl, for example 
benzoyl and substituted benzoyl wherein the benzene ring is substituted 
with from one to three substituents chosen from the group consisting of 
halogen, nitro, cyano, C.sub.1 to C.sub.6 alkyl, C.sub.1 to C.sub.6 
haloalkyl, C.sub.1 to C.sub.6 alkoxy and C.sub.1 to C.sub.6 alkylthio; and 
heteroaroyl, for example 2-furoyl, 3-furoyl, 2-thenoyl and 3-thenoyl. 
When in the compound of formula I R.sup.1 is chosen from an inorganic or 
organic cation the nature of the cation is not narrowly critical. Although 
not intending to be bound by theory, it is believed that when R.sup.1 is a 
cation the cation is removed in the plant to give a compound of formula I 
wherein R.sup.1 is hydrogen. Suitable inorganic cations include the alkali 
and alkaline earth metal ions, heavy metal ions including the transition 
metal ions, and the ammonium ion. Suitable organic cations include the 
cation R.sup.4 R.sup.5 R.sup.6 R.sup.7 N.sup..sym. wherein R.sup.4, 
R.sup.5, R.sup.6 and R.sup.7 are independently chosen from the group 
consisting of: hydrogen; C.sub.1 to C.sub.10 alkyl; substituted C.sub.1 to 
C.sub.10 alkyl wherein the alkyl group is substituted with a substituent 
chosen from the group consisting of hydroxy, halogen and C.sub.1 to 
C.sub.6 alkoxy; phenyl; benzyl; and the groups substituted phenyl and 
substituted benzyl wherein the benzene ring is substituted with from one 
to three substituents chosen from the group consisting of halogen, nitro, 
cyano, C.sub.1 to C.sub.6 alkyl, C.sub.1 to C.sub.6 haloalkyl, C.sub.1 to 
C.sub.6 alkoxy and C.sub.1 to C.sub.6 alkylthio. 
It should be recognized that when R.sup.1 is hydrogen the compounds of the 
invention may exist in any one of three tautomeric forms as shown below: 
##STR3## 
Suitable X, which may be the same or different, include: halogen; nitro; 
cyano; C.sub.1 to C.sub.6 alkyl; C.sub.1 to C.sub.6 alkyl substituted with 
a substituent selected from the group consisting of halogen, nitro and 
C.sub.1 to C.sub.6 alkoxy; hydroxy; C.sub.1 to C.sub.6 alkoxy; C.sub.1 to 
C.sub.6 alkoxy substituted with a substituent selected from halogen and 
C.sub.1 to C.sub.6 alkoxy; C.sub.2 to C.sub.6 alkanoyloxy; amino; C.sub.1 
to C.sub.6 alkylamino; di(C.sub.1 to C.sub.6 alkyl)amino; C.sub.1 to 
C.sub.6 alkanoylamino; benzoylamino; formyl; C.sub.2 to C.sub.6 alkanoyl; 
(C.sub.1 to C.sub.6 alkoxy)carbonyl; C.sub.1 to C.sub.6 alkylthio; C.sub.1 
to C.sub.6 alkylsulfinyl; C.sub.1 to C.sub.6 alkylsulfonyl; sulfamoyl; 
N-(C.sub.1 to C.sub.6 alkyl)sulfamoyl; and N,N-di(C.sub.1 to C.sub.6 
alkyl)sulfamoyl; at least two of X are methyl and at least one of X is not 
selected from the group consisting of halogen, C.sub.1 to C.sub.6 alkyl 
and C.sub.1 to C.sub.6 alkoxy. 
Suitable R.sup.1 include hydrogen, benzoyl, substituted benzoyl wherein the 
benzene ring is substituted with from one to three substituents selected 
from the group consisting of halogen, nitro, C.sub.1 to C.sub.6 alkyl, 
C.sub.1 to C.sub.6 alkoxy and C.sub.1 to C.sub.6 haloalkyl, and the group 
M wherein M is an alkali metal ion. 
Suitable R.sup.2 include C.sub.1 to C.sub.6 alkyl, C.sub.2 to C.sub.6 
alkenyl, C.sub.2 to C.sub.6 alkynyl, benzyl and substituted benzyl wherein 
the benzene ring is substituted with from one to three substituents 
selected from the group consisting of halogen, nitro, C.sub.1 to C.sub.6 
alkyl, C.sub.1 to C.sub.6 alkoxy and C.sub.1 to C.sub.6 haloalkoxy. 
Suitable R.sup.3 include C.sub.1 to C.sub.6 alkyl. 
Preferred X include: halogen; nitro; cyano; hydroxy; C.sub.1 to C.sub.4 
alkyl; C.sub.1 to C.sub.4 alkoxy; C.sub.2 to C.sub.4 alkenyloxy; C.sub.1 
to C.sub.4 alkylthio; C.sub.1 to C.sub.4 alkylsulfinyl; C.sub.1 to C.sub.4 
alkylsulfonyl; formyl, C.sub.2 to C.sub.6 alkanoyl and the oxime O-C.sub.1 
to C.sub.4 alkyl ethers thereof; C.sub.2 to C.sub.6 alkanoyloxy; 
benzyloxy; sulfamoyl; N,N-di(C.sub.1 to C.sub.4 alkyl)sulfamoyl; C.sub.1 
to C.sub.4 alkyl substituted with a substituent selected from the group 
consisting of nitro, hydroxy, C.sub.1 to C.sub.4 alkoxy and C.sub.1 to 
C.sub.4 alkylthio; C.sub.1 to C.sub.4 alkoxy substituted with one or more 
substituents selected from halogen; the group NR.sup.8 R.sup.9 wherein 
R.sup.8 and R.sup.9 are independently selected from hydrogen and C.sub.2 
to C.sub.4 alkanoyl. 
Preferred R.sup.1 include: hydrogen; C.sub.2 to C.sub.6 alkanoyl such as 
acetyl; benzoyl and substituted benzoyl wherein the benzene ring is 
substituted with from one to three substituents selected from the group 
consisting of halogen, nitro, C.sub.1 to C.sub.6 alkyl and C.sub.1 to 
C.sub.6 alkoxy, benzenesulfonyl and substituted benzenesulfonyl wherein 
the benzene ring is substituted with from one to three substituents 
selected from the group consisting of halogen, nitro, C.sub.1 to C.sub.6 
alkyl and C.sub.1 to C.sub.6 alkoxy; and an inorganic or organic cation 
selected from the cations of the alkali metals such as lithium, potassium 
and sodium, the cations of the alkaline earth metals such as magnesium, 
calcium and barium, the cations of the transition metals such as 
manganese, copper, zinc, iron, nickel, cobalt and silver, the ammonium ion 
and the tri- and tetra-(alkyl)ammonium ions wherein alkyl is selected from 
C.sub.1 to C.sub.6 alkyl and C.sub.1 to C.sub.6 hydroxyalkyl. 
Preferred R.sup.2 include: C.sub.1 to C.sub.6 alkyl; C.sub.2 to C.sub.6 
alkenyl; C.sub.2 to C.sub.6 alkynyl; C.sub.1 to C.sub.6 haloalkyl; C.sub.2 
to C.sub.6 haloalkenyl; and C.sub.2 to C.sub.6 haloalkynyl. 
Preferred R.sup.3 include C.sub.1 to C.sub.6 alkyl. 
More preferred compounds of the invention include those compounds of 
formula I in which the benzene ring is substituted in the 2- and 
6-positions. That is compounds of formula 
##STR4## 
wherein: X, X.sup.2 and X.sup.6 are independently selected from the group 
consisting of halogen, nitro, cyano, hydroxy, amino, methyl, ethyl, 
methoxy, methylmercapto, n-butylmercapto, nitromethyl, hydroxymethyl, 
methoxymethyl, ethoxymethyl, n-butylthiomethyl, difluoromethoxy, allyloxy, 
benzyloxy, methylsulfinyl, methylsulfonyl, formyl, formyl oxime O-ethyl 
ether, acetyl, butyryl, propionyl, acetyloxy, sulfamoyl, 
N,N-dimethylsulfamoyl and acetylamino, and at least one of X, X.sup.2 and 
X.sup.6 is not selected from the group consisting of halogen, methyl, 
ethyl and methoxy; R.sup.1 is selected from the group consisting of 
hydrogen, acetyl, benzoyl, nitrobenzoyl, methylbenzenesulfonyl and the 
cations of the alkali metals; 
R.sup.2 is selected from the group consisting of C.sub.1 to C.sub.3 alkyl, 
2-haloethyl, allyl and 2-haloallyl; 
R.sup.3 is selected from the group consisting of C.sub.1 to C.sub.3 alkyl; 
and 
m is an integer selected from 1 to 3. 
Preferably the substituents in the 2- and 6-positions of the benzene ring 
are independently selected from halogen, methyl, methoxy and 
methylmercapto. 
Even more preferred compounds of the invention include those compounds of 
formula I in which the benzene ring is substituted in the 2-, 3- and 
6-positions and wherein the substituents in the 2- and 6-positions are 
methyl. That is, compounds of formula 
##STR5## 
wherein: X and X.sup.3, which may be the same or different, are selected 
from the group consisting of halogen, methyl, ethyl, methoxy, 
methylmercapto, nitromethyl, hydroxymethyl, methoxymethyl, ethoxymethyl, 
methylsulfinyl, methylsulfonyl, acetyl, propionyl, sulfamoyl and 
N,N-di(methyl)sulfamoyl, and at least one of X is not selected from the 
group consisting of halogen, methyl, ethyl and methoxy; 
R.sup.1 is selected from the group consisting of hydrogen, acetyl, benzoyl, 
nitrobenzoyl, methylbenzenesulfonyl and the cations of the alkali metals; 
R.sup.2 is selected from the group consisting of C.sub.1 to C.sub.3 alkyl, 
2-haloethyl, allyl and 2-haloallyl; 
R.sup.3 is selected from the group consisting of C.sub.1 to C.sub.3 alkyl; 
and 
m is 0 or an integer selected from 1 and 2. 
Further preferred compounds of the invention include those compounds of 
formula 
##STR6## 
wherein: X.sup.3 is selected from the group consisting of methylmercapto, 
nitromethyl, methoxymethyl, ethoxymethyl, methylsulfinyl, methylsulfonyl, 
acetyl, propionyl, sulfamoyl and N,N-dimethylsulfamoyl; 
X.sup.4 is selected from hydrogen and methyl; 
X.sup.5 is selected from hydrogen, methyl and ethyl; 
R.sup.1 is selected from hydrogen, sodium and potassium; 
R.sup.2 is selected from ethyl and allyl; and 
R.sup.3 is selected from ethyl and n-propyl. 
Specific examples of the compounds of the invention include those compounds 
detailed in Table 1 below. 
TABLE 1 
__________________________________________________________________________ 
##STR7## 
Compound 
No (X).sub.m R.sup.1 
R.sup.2 R.sup.3 
__________________________________________________________________________ 
1 2,4,6-(CH.sub.3).sub.33-NO.sub.2 
H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
2 2,4,6-(CH.sub.3).sub.33,5-(NO.sub.2).sub.2 
H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
3 4-CH.sub.33,5-(NO.sub.2).sub.2 
H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
4 2,4-(CH.sub.3).sub.26-CH.sub.3 O3,5-(NO.sub.2).sub.2 
H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
5 2,6-(CH.sub.3).sub.23-SO.sub.2 N(CH.sub.3).sub.2 
H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
6 2,4,6-(CH.sub.3).sub.33-NO.sub.2 
H C.sub.2 H.sub.5 
n-C.sub.3 H.sub.7 
7 2,4,6-(CH.sub.3).sub.33-NO.sub.2 
H CH.sub.2 CHCH.sub.2 
n-C.sub.3 H.sub.7 
8 2,4,6-(CH.sub. 3).sub.33-NH.sub.2 
H C.sub.2 H.sub.5 
n-C.sub.3 H.sub.7 
9 2,4,6-(CH.sub.3).sub.33-SOCH.sub.3 
H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
10 2,4,6-(CH.sub.3).sub.33-SO.sub.2 CH.sub.3 
H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
11 2,4,6-(CH.sub.3).sub.33-SO.sub.2 N(CH.sub.3).sub.2 
H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
12 2,4,6-(CH.sub.3).sub.33-SO.sub.2 NH.sub.2 
H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
13 2,4,6-(CH.sub.3).sub.33-COCH.sub.3 
H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
14 2,4,6-(CH.sub.3).sub.33-COCH.sub.2 CH.sub.2 CH.sub.3 
H C.sub.2 H.sub.5 
n-C.sub.3 H.sub.7 
15 2,4,6-(CH.sub.3).sub.33-CHNOC.sub.2 H.sub.5 
H C.sub.2 H.sub.5 
n-C.sub.3 H.sub.7 
16 2,4,6-(CH.sub.3).sub.33-CH.sub.3 O5-NO.sub.2 
H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
17 2,4,6-(CH.sub.3).sub.33-Br5-NO.sub.2 
H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
18 2,5,6-(CH.sub.3).sub.33-O.sub.2 NCH.sub.2 
H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
19 3,4,5-(CH.sub.3).sub. 32,6-(NO.sub.2).sub.2 
H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
20 2,3,4,6-(CH.sub.3).sub.45-NO.sub.2 
H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
21 4-HO3,5-(NO.sub.2).sub.2 
H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
22 2,4,6-(CH.sub.3).sub.33-COCH.sub.35-C.sub.2 H.sub.5 
H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
23 2,6-(CH.sub.3).sub.23-NO.sub.2 
H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
24 2,3,5,6-(CH.sub.3).sub.44-COCH.sub.3 
H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
25 2,4,6-(CH.sub.3).sub.33-NHCOCH.sub.3 
H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
26 2,4,6-(CH.sub.3).sub.33-CN 
H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
27 2,3,4,6-(CH.sub.3).sub.45-COCH.sub.3 
H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
28 2,4-(CH.sub.3).sub.23-Cl6-OCF.sub.2 H 
H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
29 2,3,4,5-(CH.sub.3).sub.46-SCH.sub.3 
H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
30 2,3,5,6-(CH.sub.3).sub.44-SCH.sub.3 
H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
31 2,6-(CH.sub.3).sub.24-OH 
H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
32 2,3,4,5-(CH.sub.3).sub.46-SCH.sub.3 
H C.sub.2 H.sub.5 
n-C.sub.3 H.sub.7 
33 2,3,5,6-(CH.sub.3).sub.44-SCH.sub.3 
H C.sub.2 H.sub.5 
n-C.sub.3 H.sub.7 
34 2,6-(CH.sub.3).sub.24-O.sub.2 CCH.sub.3 
H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
35 2,4,6-(CH.sub.3).sub.33-COC.sub.2 H.sub.5 
H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
36 2,3,5,6-(CH.sub.3).sub.44-OH 
H C.sub.2 H.sub.5 
n-C.sub.3 H.sub.7 
37 2,4-(CH.sub.3).sub.26-OH 
H C.sub.2 H.sub.5 
n-C.sub.3 H.sub.7 
38 2,3,4,6-(CH.sub.3).sub.45-CH.sub.2 OCH.sub.3 
H C.sub.2 H.sub.5 
n-C.sub.3 H.sub.7 
39 2,3,5,6-(CH.sub.3).sub.44-SC.sub.4 H.sub.9n 
H C.sub.2 H.sub.5 
n-C.sub.3 H.sub.7 
40 2,4,6-(CH.sub.3).sub.33-CH.sub.2 OCH.sub.3 
H C.sub.2 H.sub.5 
n-C.sub.3 H.sub.7 
41 2,4,6-(CH.sub.3).sub.33-CH.sub.2 OC.sub.2 H.sub.5 
H C.sub.2 H.sub.5 
n-C.sub.3 H.sub.7 
42 2,4-(CH.sub.3).sub.26-OCF.sub.2 H 
H C.sub.2 H.sub.5 
n-C.sub.3 H.sub.7 
43 2,4,6-(CH.sub.3).sub.33-COCH.sub.3 
H C.sub.2 H.sub.5 
n-C.sub.3 H.sub.7 
44 2,3,4,5-(CH.sub.3).sub.46-SCH.sub.3 
Na.sup..sym. 
C.sub.2 H.sub.5 
n-C.sub.3 H.sub.7 
45 2,3,4,5-(CH.sub.3).sub.46-SCH.sub.3 
H CH.sub.2 CBrCH.sub.2 
n-C.sub.3 H.sub.7 
46 2,3,4,5-(CH.sub.3).sub.46-SCH.sub.3 
1/2Cu .circle..sup.2+ 
C.sub.2 H.sub.5 
n-C.sub.3 H.sub.7 
47 2,3,4,5-(CH.sub.3).sub.46-SCH.sub.3 
a C.sub.2 H.sub.5 
n-C.sub.3 H.sub.7 
48 2,3,5,6-(CH.sub.3).sub.44-OCH.sub.2C.sub.6 H.sub.5 
H C.sub.2 H.sub.5 
n-C.sub.3 H.sub.7 
49 2,6-(CH.sub.3).sub.24-OCH.sub.2 C.sub.6 H.sub.5 
H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
50 2,4-(CH.sub.3).sub.26-OCH.sub.2 C.sub.6 H.sub.5 
H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
51 2,4,6-(CH.sub.3).sub.33-CH.sub.2 OH 
H C.sub.2 H.sub.5 
n-C.sub.3 H.sub.7 
52 2,3,5,6-(CH.sub.3).sub.44-OCH.sub.2 CHCH.sub.2 
H C.sub.2 H.sub.5 
n-C.sub.3 H.sub.7 
53 2,3,4,5-(CH.sub.3).sub.46-SCH.sub.3 
H CH.sub.2 CH.sub.2 F 
n-C.sub.3 H.sub.7 
54 2,4,6-(CH.sub.3).sub.33-COCH.sub.3 
Na.sup..sym. 
C.sub.2 H.sub.5 
n-C.sub.3 H.sub.7 
55 2,4,6-(CH.sub.3).sub.33-COCH.sub.3 
b C.sub.2 H.sub.5 
n-C.sub.3 H.sub.7 
56 2,4,6-(CH.sub.3).sub.33-COCH.sub.3 
c C.sub.2 H.sub.5 
n-C.sub.3 H.sub.7 
57 2,3,4,5-(CH.sub.3).sub.46-SO.sub.2 CH.sub.3 
H C.sub.2 H.sub.5 
n-C.sub.3 H.sub.7 
58 2,3,4,5-(CH.sub.3).sub.46-SCH.sub.3 
COCH.sub.3 
C.sub.2 H.sub.5 
n-C.sub.3 H.sub.7 
59 2,4,6-(CH.sub.3).sub.33-CH.sub.2 SC.sub.4 H.sub.9n 
H C.sub.2 H.sub.5 
n-C.sub.3 H.sub.7 
60 2,4,6-(CH.sub.3).sub.33-OCF.sub.2 H 
H C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
__________________________________________________________________________ 
Footnotes to Table 1 
a C.sub.6 H.sub.5 CO 
b 4CH.sub.3 C.sub.6 H.sub.4 SO.sub.2 
c 4NO.sub.2 C.sub.6 H.sub.4 CO 
The compounds of the invention may be prepared by a variety of methods and 
in a further aspect the invention provides methods for the preparation of 
compounds of formula I. 
Conveniently the preparation of the compounds of the invention can be 
considered in three or four parts. 
Part A involves the formation of a 5-(substituted 
phenyl)cyclohexane-1,3-dione of formula IX. This reaction may be carried 
out in a two step process by condensing a benzaldehyde derivative of 
formula V with acetone to form a ketone of formula VI, which is in turn 
condensed with a malonic acid ester of formula VII to give a 
5-(substituted phenyl)cyclohexane-1,3-dione of formula IX, either with or 
without the isolation of the intermediate of formula VIII. 
Alternatively, this preparation may be carried out in a two step process by 
condensing a benzaldehyde derivative of formula V with a malonic acid 
ester of formula VII to give a benzylidenemalonate derivative of formula X 
which is in turn condensed with an acetoacetic acid ester of formula XI to 
give a 5-(substituted phenyl)cyclohexane-1,3-dione of formula IX, either 
with or without isolation of the intermediate of formula XII. 
In a further alternative process this preparation may be carried out by 
condensing a cinnamate of formula XXI with an acetoacetic acid ester of 
formula XI to give a 5-(substituted phenyl)cyclohexane-1,3-dione of 
formula IX, either with or without isolation of the intermediate of 
formula VIII. 
The above reaction sequences are set out in SCHEME A parts (i), (ii) and 
(iii) respectively below, wherein R represents a C.sub.1 to C.sub.6 alkyl 
group. 
##STR8## 
Part B involves the acylation of a compound of formula IX to give a 
2-acyl-5-(substituted phenyl)cyclohexane-1,3-dione of formula XIII. This 
reaction may be carried out by reacting a 5-(substituted 
phenyl)cyclohexane-1,3-dione of formula IX with: 
(iv) a mixture of an acid anhydride of formula XIV and either a salt of 
that acid or an alkoxide salt wherein M is an alkali metal ion and R is 
C.sub.1 to C.sub.6 alkyl; 
(v) a mixture of an acid anhydride of formula XIV and the corresponding 
acid; 
(vi) an acid halide of formula XV; or 
(vii) a mixture of an acid halide of formula XV and the corresponding acid; 
(viii) an alkali metal or alkaline earth metal hydride followed by reaction 
with an acid anhydride of formula XIV or an acid halide of formula XV. 
Alternatively this reaction may be carried out by: 
(ix) reacting a 5-(substituted phenyl)cyclohexane-1,3-dione of formula IX 
with an acid halide of formula XV in the presence of pyridine to give an 
intermediate O-acyl derivative of formula XVI; and then: 
(x) reacting the intermediate of formula XVI with a Lewis acid catalyst; 
(xi) reacting the intermediate of formula XVI with the corresponding acid 
of the acid halide of formula XV; or 
(xii) reacting the intermediate of formula XVI with imidazole. 
Each of these reactions is outlined in SCHEME B below wherein hal 
represents halogen. 
##STR9## 
Part C involves the formation of a compound of the invention of formula I 
wherein R.sup.1 is hydrogen, that is a compound of formula II. This 
reaction may be carried out either: 
(xiii) by reacting a compound of formula XIII with an alkoxyamine 
derivative of formula XVII to give a compound of formula II; or 
(xiv) by reacting a compound of formula XIII with hydroxylamine to give an 
intermediate oxime derivative of formula XVIII and reacting the oxime 
derivative of formula XVIII with an alkylating agent of formula XIX to 
give a compound of formula II. 
These reaction sequences are set out in SCHEME C below wherein L is a good 
leaving group such as, for example, chloride, bromide, iodide, sulfate, 
nitrate, methyl sulfate, ethyl sulfate, tetrafluoroborate, 
hexafluorophosphate, hexafluoroantimonate, methanesulfonate, 
fluorosulfonate, fluoromethanesulfonate and trifluoromethanesulfonate. 
##STR10## 
Compounds of the invention of formula I wherein R.sup.1 is not hydrogen may 
be prepared from compounds of the invention of formula I wherein R.sup.1 
is hydrogen, that is, compounds of formula II, by acylation etherification 
or sulfonylation as required. This reaction is outlined in SCHEME D below. 
##STR11## 
Compounds of the invention of formula I wherein R.sup.1 is an inorganic or 
organic cation may be prepared from the compounds of the invention of 
formula I wherein R.sup.1 is hydrogen, that is, compounds of formula II, 
by reacting said compounds of formula II with an inorganic or organic 
salt. For example, the compounds of formula I wherein R.sup.1 is an alkali 
metal ion may be prepared by reacting the appropriate compound of formula 
II with the appropriate alkali metal hydroxide or alkoxylate. The 
compounds of formula I wherein R.sup.1 is a transition metal ion or an 
organic cation may similarly be prepared by reacting the appropriate 
compound of formula II with an appropriate transition metal salt or 
organic base. Alternatively, the compounds of formula I wherein R.sup.1 is 
a transition metal ion or an organic cation may be prepared by reacting 
the appropriate compound of formula I wherein R.sup.1 is an alkali metal 
ion with an appropriate transition metal salt or organic salt. 
Accordingly, in a further aspect the invention provides a process for the 
preparation of a compound of formula I, wherein X, R.sup.1, R.sup.2, 
R.sup.3 and m are as hereinbefore defined, which process comprises: 
(a) reacting a benzaldehyde derivative of formula V with acetone to give a 
ketone derivative of formula VI and reacting the ketone derivative of 
formula VI with malonic acid ester of formula VII, wherein R is C.sub.1 to 
C.sub.6 alkyl, to give a 5-(substituted phenyl)cyclohexane-1,3-dione 
derivative of formula IX; or reacting a benzaldehyde derivative of formula 
V with a malonic acid ester of formula VII to give a benzylidenemalonate 
derivative of formula X and reacting the benzylidenemalonate derivative of 
formula X with an acetoacetic acid ester of formula XI, wherein R is 
C.sub.1 to C.sub.6 alkyl, to give a 5-(substituted 
phenyl)cyclohexane-1,3-dione derivative of formula IX; or reacting a 
cinnamate of formula XXI, wherein R is C.sub.1 to C.sub.6 alkyl, with an 
acetoacetic acid ester of formula XI, wherein R is C.sub.1 to C.sub.6 
alkyl, to give a 5-(substituted phenyl)cyclohexane-1,3-dione derivative of 
formula IX; 
(b) acylating the 5-(substituted phenyl)cyclohexane-1,3-dione derivative of 
formula IX with an acid anhydride of formula XIV or an acid halide of 
formula XV to give a 2-acyl-5-(substituted phenyl)cyclohexane-1,3-dione 
derivative of formula XIII; 
(c) reacting the 2-acyl-5-(substituted phenyl)cyclohexane-1,3-dione 
derivative of formula XIII with an alkoxyamine derivative of formula XVII 
to give a compound of the invention of formula II or reacting the 
2-acyl-5-(substituted phenyl)cyclohexane-1,3-dione derivative of formula 
XIII with hydroxylamine and alkylating the oxime intermediate of formula 
XVIII with an alkylating agent of formula XIX, wherein L is a good leaving 
group, to give a compound of the invention of formula II; and 
(d) reacting the compound of the invention of formula II with a compound of 
formula XX, wherein L is a good leaving group, to give a compound of the 
invention of formula I. 
Certain of the intermediate compounds of formulae VI, VIII, IX, X, XII, 
XIII, XVI and XVIII are novel compounds and therefore as a further 
embodiment the invention provides novel compounds of formulae VI, VIII, 
IX, X, XII, XXI, XIII, XVI and XVIII, wherein the substituents are as 
hereinbefore defined, and processes for the preparation thereof. 
The compounds of formula I are active as herbicides and therefore, in a 
further aspect the invention provides a process for severely damaging or 
killing unwanted plants which process comprises applying to the plants, or 
to the growth medium of the plants, an effective amount of a compound of 
formula I as hereinbefore defined. 
Generally speaking the compounds of formula I are herbicidally effective 
against monocotyledonous plants, or grasses. However, certain of the 
compounds of formula I are selectively active within the group of 
monocotyledonous plants and may be used at a rate sufficient to kill or 
severely damage monocotyledonous weeds in a monocotyledonous cereal crop. 
Therefore, in yet a further aspect the invention provides a process for 
selectively controlling the growth of weeds in crops which process 
comprises applying to the crop, or to the growth medium of the crop, a 
compound of formula I, as hereinbefore defined, in an amount sufficient to 
severely damage or kill the weeds but insufficient to damage the crop 
substantially. 
The compounds of the present invention of formula I have three or more 
substituents in the phenyl ring located in the 5-position of the 
cyclohexane ring. Surprisingly, among the compounds of the invention which 
show highest herbicidal activity are those compounds of formula I in which 
the phenyl group is substituted in the 2- and 6-positions. More 
surprisingly, among the more preferred or more active compounds are those 
compounds of formula I in which the phenyl group is substituted in the 2-, 
3- and 6-positions. 
The compounds of formula I may be applied directly to the plant 
(post-emergence application) or to the soil before the emergence of the 
plant (pre-emergence application). However, the compounds are, in general, 
more effective when applied to the plant post-emergence. 
The compounds of formula I may be used on their own to inhibit the growth 
of, severely damage, or kill plants but are preferably used in the form of 
a composition comprising a compound of the invention in admixture with a 
carrier comprising a solid or liquid diluent. Therefore, in yet a further 
aspect the invention provides plant growth inhibiting, plant damaging, or 
plant killing compositions comprising a compound of formula I as 
hereinbefore defined and an inert carrier therefor. 
Certain of the compounds of formula I exhibit useful plant growth 
regulating activity. For example, while certain compounds of formula I 
show selective herbicidal activity against wild grasses in crops of 
cultivated plants, at some rates of application they exhibit plant growth 
regulating effects in said crops. 
Plant growth regulating effects may be manifested in a number of ways. For 
example, suppression of apical dominance, stimulation of auxiliary bud 
growth, stimulation of early flowering and seed formation, enhancement, of 
flowering and increase in seed yield, stem thickening, stem shortening and 
tillering. Plant growth regulating effects shown by compounds of the 
invention include, for example, tillering and stem shortening in crops 
such as wheat and barley. 
Accordingly in a still further aspect the invention provides a process for 
regulating the growth of a plant which process comprises applying to the 
plant, to the seed of the plant, or to the growth medium of the plant, an 
effective amount of a compound of formula I, as hereinbefore defined. 
To effect the plant growth regulating process of the present invention the 
compounds of formula I may be applied directly to the plant 
(post-emergence application) or to the seed or soil before the emergence 
of the plant (pre-emergence) application. 
The compounds of formula I may be used on their own to regulate the growth 
of plants but in general are preferably used in the form of a composition 
comprising a compound of the invention in admixture with a carrier 
comprising a solid or liquid dilent. Therefore, in a still further aspect 
the invention provides plant growth regulating compositions comprising a 
compound of formula I as hereinbefore defined an an inert carrier 
therefor. 
The compositions of the present invention may be in the form of solids, 
liquids or pastes. The compositions include both dilute compositions which 
are ready for immediate use and concentrated compositions which may 
require dilution before use. Therefore, the concentration of the active 
ingredient in the compositions of the present invention will vary 
depending on the type of formulation and whether the composition is ready 
for use such as, for example, a dust formulation or an aqueous emulsion or 
whether the composition is a concentrate such as, for example, an 
emulsifiable concentrate or a wettable powder, which is suitable for 
dilution before use. In general the compositions of the present invention 
comprise from 1 ppm to 99% by weight of active ingredient. 
The solid compositions may be in the form of powders, dusts, pellets, 
grains, and granules wherein the active ingredient is mixed with a solid 
diluent. Powders and dusts may be prepared by mixing or grinding the 
active ingredient with a solid carrier to give a finely divided 
composition. Granules, grains and pellets may be prepared by bonding the 
active ingredient to a solid carrier, for example, by coating or 
impregnating the preformed granular solid carrier with the active 
ingredient or by agglomeration techniques. 
Examples of solid carriers include: mineral earths and clays such as, for 
example, kaolin, bentonite, kieselguhr, Fuller's earth, Attaclay, 
diatomaceous earth, bole, loess, talc, chalk, dolomite, limestone, lime, 
calcium carbonate, powdered magnesia, magnesium oxide, magnesium sulfate, 
gypsum, calcium sulfate, pyrophyllite, silicic acid, silicates and silica 
gels; fertilizers such as, for example, ammonium sulfate, ammonium 
phosphate, ammonium nitrate and urea; natural products of vegetable origin 
such as, for example, grain meals and flours, bark meals, wood meals, 
nutshell meals and cellulosic powders; and synthetic polymeric materials 
such as, for example, ground or powdered plastics and resins. 
Alternatively, the solid compositions may be in the form of dispersible or 
wettable dusts, powders, granules or grains wherein the active ingredient 
and the solid carrier are combined with one or more surface active agents 
which act as wetting, emulsifying and/or dispersing agents to facilitate 
the dispersion of the active ingredient in liquid. 
Examples of surface active agents include those of the cationic, anionic 
and non-ionic type. Cationic surface active agents include quaternary 
ammonium compounds, for example, the long chain alkylammonium salts such 
as cetyltrimethylammonium bromide. Anionic surface active agents include: 
soaps or the alkali metal, alkaline earth metal and ammonium salts of 
fatty acids; the alkali metal, alkaline earth metal and ammonium salts of 
ligninsulfonic acid; the alkali metal, alkaline earth metal and ammonium 
salts of arylsulfonic acids including the salts of naphthalenesulfonic 
acids such as butylnaphthalenesulfonic acid, the di- and 
tri-isopropylnaphthalenesulfonic acids, the salts of the condensation 
products of sulfonated naphthalene and naphthalene derivatives with 
formaldehyde, the salts of the condensation products of sulfonated 
naphthalene and naphthalene derivatives with phenol and formaldehyde, and 
the salts of alkylarylbenzenesulfonic acids such as dodecylbenzenesulfonic 
acid; the alkali metal, alkaline earth metal and ammonium salts of the 
long chain mono esters of sulfuric acid or alkylsulfates such as 
laurylsulfate and the mono esters of sulfuric acid with fatty alcohol 
glycol ethers. Nonionic surface active agents include: the condensation 
products of ethylene oxide with fatty alcohols such as oleyl alcohol and 
cetyl alcohol; the condensation products of ethylene oxide with phenols 
and alkylphenols such as isooctylphenol, octylphenol and nonylphenol; the 
condensation products of ethylene oxide with castor oil; the partial 
esters derived from long chain fatty acids and hexitol anhydrides, for 
example sorbitan monolaurate, and their condensation products with 
ethylene oxide; ethylene oxide/propylene oxide block copolymers; lauryl 
alcohol polyglycol ether acetal; and the lecithins. 
The liquid compositions may comprise a solution or dispersion of the active 
ingredient in a liquid carrier optionally containing one or more surface 
active agents which act as wetting, emulsifying and/or dispersing agents. 
Examples of liquid carriers include: water; mineral oil fractions such as, 
for example, kerosene, solvent naphtha, petroleum, coal tar oils and 
aromatic hydrocarbons such as, for example, paraffin, cyclohexane, 
toluene, the xylenes, tetrahydronaphthalene and alkylated naphthalenes; 
alcohols such as, for example, methanol, ethanol, propanol, isopropanol, 
butanol, cyclohexanol and propylene glycol; ketones such as, for example, 
cyclohexanone and isophorone; and strongly polar organic solvents such as, 
for example, dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone and 
sulfolane. 
A preferred liquid composition comprises an aqueous suspension, dispersion 
or emulsion of the active ingredient which is suitable for application by 
spraying, atomizing or watering. Such aqueous compositions are generally 
prepared by mixing concentrated compositions with water. Suitable 
concentrated compositions include emulsion concentrates, pastes, oil 
dispersions, aqueous suspensions and wettable powders. The concentrates 
are usually required to withstand storage for prolonged periods and after 
such storage to be capable of dilution with water to form aqueous 
preparations which remain homogeneous for a sufficient time to enable them 
to be applied by conventional spray equipment. The concentrates 
conveniently contain from 20 to 99%, preferably 20 to 60%, by weight of 
active ingredient. 
Emulsion or emulsifiable concentrates are conveniently prepared by 
dissolving the active ingredient in an organic solvent containing one or 
more surface active agents. Pastes may be prepared by blending the finely 
divided active ingredient with a finely divided solid carrier, one or more 
surface active agents and optionally an oil. Oil dispersions may be 
prepared by grinding together the active ingredients, a hydrocarbon oil, 
and one or more surface active agents. Aqueous suspension concentrates may 
conveniently be prepared by ball milling a mixture of the active 
ingredient, water, at least one surface active agent and preferably at 
least one suspending agent. Suitable suspending agents include: 
hydrophilic colloids such as, for example, poly(N-vinylpyrrolidone), 
sodium carboxymethylcellulose and the vegetable gums gum acacia and gum 
tragacanth; hydrated colloidal mineral silicates such as, for example, 
montmorillonite, beidellite, nontronite, hectorite, saponite, sauconite 
and bentonite; other cellulose derivatives; and poly(vinyl alcohol). 
Wettable powder concentrates may conveniently be prepared by blending 
together the active ingredient, one or more surface active agents, one or 
more solid carriers and optionally one or more suspending agents and 
grinding the mixture to give a powder having the required particle size. 
The aqueous suspension, dispersions or emulsions may be prepared from the 
concentrated compositions by mixing the concentrated compositions with 
water optionally containing surface active agents and/or oils. 
It should be noted that the compounds of the invention of formula I wherein 
R.sup.1 is hydrogen are acidic. Therefore, the compounds of formula I may 
be formulated and applied as the salts of organic or inorganic bases. In 
formulating and employing the compounds of formula I in the form of their 
salts, either the salts per se, that is the compounds of formula I wherein 
R.sup.1 is an inorganic or an organic cation, may be used in the 
formulation or the compounds of formula I wherein R.sup.1 is hydrogen may 
be used in the formulation and the salts generated in situ by the use of 
the appropriate organic or inorganic base. 
The mode of application of the compositions of the invention will depend to 
a large extent on the type of composition used and the facilities 
available for its application. Solid compositions may be applied by 
dusting or any other suitable means for broadcasting or spreading the 
solid. Liquid compositions may be applied by spraying, atomizing, 
watering, introduction into the irrigation water, or any other suitable 
means for broadcasting or spreading the liquid. 
The rate of application of the compounds of the invention will depend on a 
number of factors including, for example, the compound chosen for use, the 
identity of the plants whose growth is to be inhibited the formulations 
selected for use and whether the compound is to be applied for foliage or 
root uptake. As a general guide, however, an application rate of from 
0.005 to 20 kilograms per hectare is suitable while from 0.01 to 5.0 
kilograms per hectare may be preferred. 
The compositions of the invention may comprise, in addition to one or more 
compounds of the invention, one or more compounds not of the invention but 
which possess biological activity. For example, as hereinbefore indicated 
the compounds of the invention are in general substantially more effective 
against monocotyledonous plants or grass species than against 
dicotyledonous plants or broad-leaved species. As a result, in certain 
applications the herbicidal use of the compounds of the invention alone 
may not be sufficient to protect a crop. Accordingly in yet a still 
further embodiment the invention provides a herbicidal composition 
comprising a mixture of at least one herbicidal compound of formula I as 
hereinbefore defined with at least one other herbicide. 
The other herbidide may be any herbicide not having the formula I. It will 
generally be a herbicide having a complementary action. For example, one 
preferred class is of mixtures comprising a herbicide active against 
broad-leaved weeds. A second preferred class is of mixtures comprising a 
contact herbicide. 
Examples of useful complementary herbicides include: 
A. benzo-2,1,3-thiadiazin-4-one-2,2-dioxides such as 
3-isopropylbenzo-2,1,3-thiadiazin-4-one-2,2-dioxide (common name 
bentazon); 
B. hormone herbicides and in particular the phenoxyalkanoic acids such as 
4-chloro-2-methylphenoxy acetic acid (common name MCPA), 
2-(2,4-dichlorophenoxy)propionic acid (common name dichlorprop), 
2,4,5-trichlorophenoxyacetic acid (common name 2,4,5-T), 
4-(4-chloro-2-methylphenoxy)butyric acid (common name MCPB), 
2,4-dichlorophenoxyacetic acid (common name 2,4-D), 
4-(2,4-dichlorophenoxy)butyric acid (common name 2,4-DB), 
2-(4-chloro-2-methylphenoxy)propionic acid (common name mecoprop), and 
their derivatives (eg salts, esters, amides and the like); 
C. 3-[4-(4-halophenoxy)phenyl]-1,1-dialkylureas such as 
3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea (common name chloroxuron); 
D. dinitrophenols and their derivatives (eg acetates) such as 
2-methyl-4,6-dinitrophenol (common name DNOC), 
2-tertiarybutyl-4,6-dinitrophenol (common name dinoterb), 
2-secondarybutyl-4,6-dinitrophenol (common name dinoseb) and its ester 
dinoseb acetate; 
E. dinitroaniline herbicides such as 
N',N'-diethyl-2,6-dinitro-4-trifluoromethyl-m-phenylenediamine (common 
name dinitramine), 2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline 
(common name trifluralin) and 
4-methylsulfonyl-2,6-dinitro-N,N-dipropylaniline (common name nitralin); 
F. phenylurea herbicide such as N'-(3,4-dichlorophenyl)-N,N-dimethylurea 
(common name diuron) and N,N-dimethyl-N'--[3-(trifluoromethyl)phenyl]urea 
(common name fluometuron); 
G. phenylcarbamoyloxyphenylcarbamates such as 
3-[(methoxycarbonyl)amino]phenyl (3-methylphenyl)carbamate (common name 
phenmedipham) and 3-[(ethoxycarbonyl)amino]phenyl phenylcarbamate (common 
name desmedipham); 
H. 2-phenylpyridazin-3-ones such as 
5-amino-4-chloro-2-phenylpyridazin-3-one (common name pyrazon); 
I. uracil herbicides such as 3-cyclohexyl-5,6-trimethyleneuracil (common 
name lenacil), 5-bromo-3-sec-butyl-6-methyluracil (common name bromacil) 
and 3-tert-butyl-5-chloro-6-methyluracil (common name terbacil); 
J. triazine herbicides such as 
2-chloro-4-ethylamino-6-(iso-propylamino)-1,3,5-triazine (common name 
atrazine), 2-chloro-4,6-di(ethylamino)-1,3,5-triazine (common name 
simazine) and 2-azido-4-(iso-propylamino)-6-methylthio-1,3,5-triazine 
(common name aziproptryne); 
K. 1-alkoxy-2-alkyl-3-phenylurea herbicides such as 
3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea (common name linuron), 
3-(4-chlorophenyl)-1-methoxy-1-methylurea (common name monolinuron) and 
3-(4-bromo-4-chlorophenyl)-1-methoxy-1-methylurea (common name 
chlorobromuron); 
L. thiolcarbamate herbicides such as S-propyl dipropylthiocarbamate (common 
name verolate); 
M. 1,2,4-triazin-5-one herbicides such as 
4-amino-4,5-dihydro-3-methyl-6-phenyl-1,2,4-triazine-5-one (common name 
metamitron) and 
4-amino-6-terty-butyl-4,5-dihydro-3-methylthio-1,3,4-triazin-5-one (common 
name metribuzin); 
N. benzoic acid herbicides such as 2,3,6-trichlorobenzoic acid (common name 
2,3,6-TBA), 3,6-dichloro-2-methoxybenzoic acid (common name dicamba) and 
3-amino-2,5-dichlorobenzoic acid (common name chloramben); 
O. anilide herbicides such as 
N-butoxymethyl-.alpha.-chloro-2',6'-diethylacetanilide (common name 
butachlor), the corresponding N-methoxy compound (common name alachlor), 
the corresponding N-iso-propyl compound (common name propachlor) and 
3',4'-dichloropropionanilide (common name propanil); 
P. dihalobenzonitrile herbicides such as 2,6-dichlorobenzonitrile (common 
name dichlobenil), 3,5-dibromo-4-hydroxybenzonitrile (common name 
bromoxynil) and 3,5-diiodo-4-hydroxybenzonitrile (common name ioxynil); 
Q. haloalkanoic herbicides such as 2,2-dichloropropionic acid (common name 
delapon), trichloroacetic acid (common name TCA) and salts thereof; 
R. diphenylether herbicides such as 4-nitrophenyl 
2-nitro-4-trifluoromethylphenyl ether (common name fluorodifen), methyl 
5-(2,4-dichlorophenoxy)-2-nitrobenzoate (common name bifenox), 
2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)benzoic acid and 
2-chloro-4-trifluoromethylphenyl 3-ethoxy-4-nitrophenyl ether; 
S. N-(heteroarylaminocarbonyl)benzenesulfonamides such as 
2-chloro-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]benzenesu 
lfonamide (commonly known as DPX 4189); and 
T. miscellaneous herbicides including N,N-dimethyldiphenylacetamide (common 
name diphenamid), N-(1-naphthyl)phthalamic acid (common name naptalam) and 
3-amino-1,2,4-triazole. 
Examples of useful contact herbicides include: 
U. bipyridylium herbicides such as those in which the active entity is the 
1,1'-dimethyl-4,4'-dipyridylium ion (common name paraquat) and those in 
which the active entity is the 1,1'-ethylene 2,2'-dipyridylium ion (common 
name diquat); 
V. organoarsenical herbicides such as monosodium methanearsonate (common 
name MSMA); and 
W. amino acid herbicides such as N-(phosphonomethyl)glycine (common name 
glyphosate) and its salts and esters.