Herbicidal compositions of acylated 1,3-dicarbonyl herbicides and phenoxyalkanoic acids, salts, amides and esters therof as antidotes

This invention embodies a two-part herbicidal system comprised of an acylated 1,3-dicarbonyl herbicide compound corresponding to the formula ##STR1## and tautomeric forms thereof where R is an aromatic moiety, optionally substituted, and a non-phytotoxic antidotally effective amount of an antidote therefor selected from the group of phenoxyalkanoic acids, including salts, esters and amides thereof for use on various crops.

FIELD OF THE INVENTION 
This invention relates to herbicide compositions and methods of use, and 
more particularly, to certain herbicidal compositions comprising 
substituted acylated 1,3-dicarbonyl and 1,3,5-tricarbonyl compounds and as 
antidotes therefor substituted phenoxy alkanoic acids, their salts and 
esters, including amides. 
BACKGROUND OF THE INVENTION 
An herbicide is a compound which adversely controls or modifies plant 
growth, e.g., killing, retarding, defoliating, desiccating, bleaching, 
regulating, stunting, tillering, stimulating and dwarfing and otherwise 
adversely alter physiological plant processes. The term "plant" refers to 
all physical parts of a plant, including seeds, seedlings, saplings, 
roots, tubers, stems, stalks, foliage, and fruits. "Plant growth" includes 
all phases of development from seed germination to natural or induced 
cessation of life. 
Herbicides are generally used to control or eradicate weed pests. They have 
gained a high degree of commercial success because it has been shown that 
such control can increase crop yield and reduce harvesting costs when 
weeds are not present in the field to complicate and reduce yield. 
The most popular methods of herbicide application include: pre-plant 
incorporation into the soil; in-furrow application to seeds and 
surrounding soil; pre-emergence surface treatment of seeded soil; 
post-emergence treatment of the emerged and growing plant and soil; and 
pre-plant seed treatment. The preferred method of application is the 
post-emergence method whereby contact, translocation and residual 
herbicidal activity are in effect. 
A manufacturer of an herbicide generally recommends a range of application 
rates and concentrations calculated to maximize weed control. The range of 
rates varies from approximately 0.01 to 50 pounds per acre (0.0111 to 56 
kilograms per hectare [Kg/ha]), and is usually in the range of from 0.1 to 
25 pounds per acre (0.112 to 28 Kg/ha). The term "herbicidally effective 
amount" describes an amount of an herbicide compound which adversely 
controls or modifies plant growth. The actual amount used depends upon 
several considerations, including particular weed susceptibility and 
overall cost limitations. 
An important factor influencing the usefulness of a given herbicide is its 
selectivity towards crops. In some cases, a beneficial crop is susceptible 
to the effects of the herbicide. In addition, certain herbicidal compounds 
are phytotoxic to some weed species but not to others. To be effective, an 
herbicide must cause minimal damage (preferably no damage) to the 
beneficial crop while maximizing damage to weed species which infest the 
locus of the crop. 
To preserve the beneficial aspects of herbicide use and to minimize crop 
damage, many herbicide antidotes have been prepared. These antidotes 
reduce or eliminate damage to the crop without substantially impairing the 
damaging effect of the herbicide on weed species. See, for example, U.S. 
Pat. Nos. 4,021,224, 4,021,229 and 4,230,874. 
The precise mechanism by which an antidote reduces herbicidal crop injury 
has not been established. An antidote compound may be a remedy, 
interferent, protectant, or antagonist. As used herein, "antidote" 
describes a compound which has the effect of establishing herbicide 
selectivity, i.e., continue herbicidal phytotoxicity to weed species by 
the herbicide, and reduced or non-phytotoxicity to the cultivated crop 
species. The term "antidotally effective amount" describes an amount of an 
antidote compound which counteracts to some degree a phytotoxic response 
of a beneficial crop to an herbicide. 
Acylated 1,3-dicarbonyl compounds have been found to be very effective 
herbicides with broad general herbicidal activity against a wide range of 
plant species. The method of controlling vegetation with the compounds 
comprises applying an herbicidally effective amount of the compounds, 
usually with an inert carrier, to the area where herbicidal control is 
desired. However, the herbicidal acylated 1,3-dicarbonyl compounds have 
been found in some instances to adversely affect or interfere with the 
cultivation of a variety of crops. Therefore, the effective use of these 
herbicides for controlling weeds in the presence of such crops is further 
enhanced by, or may require in many instances, the addition of an 
antidotally effective amount of a compound, which is antidotally effective 
with the herbicide. 
DESCRIPTION OF THE INVENTION 
It has now been discovered that certain compounds, broadly defined as 
aryloxyalkanoic acids, salts, amides or esters, when used in an 
antidotally effective amount are effective antidotes for the protection of 
a variety of crops from adverse herbicidal injury or the reduction of 
adverse herbicidal injury caused by the use of an herbicidally effective 
amount of an acylated 1,3-dicarbonyl carbocyclic or heterocyclic 
herbicidal compound. 
DESCRIPTION OF THE HERBICIDE COMPOUNDS 
The acylated 1,3-dicarbonyl herbicide compounds of this invention are 
contained within and correspond to the following general formula 
##STR2## 
in which R is a group as hereinafter defined (and may generally be an 
optionally substituted aromatic moiety). Compounds of this type have been 
described in a number of references as being useful, for instance, as 
chemical intermediates and/or pesticides. The undefined remainder of the 
molecule represented in Formula A, which includes the dicarbonyl group, 
has a generally cyclical structure. 
Acylated carbocyclic 1,3-dicarbonyl compounds of this type have the general 
structure 
##STR3## 
in which R is an optionally substituted aromatic moiety as hereinafter 
defined and n is 2 or 3, preferably 3. The ring can be unsubstituted (all 
X and Y groups are hydrogen), or one or more hydrogen atoms may be 
replaced by aliphatic, aromatic, heterocyclic or alkylene groups, 
particularly hydrocarbyl groups. Examples of such hydrocarbyl groups are 
alkyl, particularly lower alkyl, phenyl, and C.sub.2 -C.sub.5 alkylene 
groups such as dimethylene, trimethylene and the like, in which case the 
compounds have a spiro structure. The carbocyclic ring may be saturated or 
unsaturated, containing an olefinic bond linking the 4- and 5-carbon 
atoms. 
Acylated heterocyclic 1,3-dicarbonyl herbicide compounds of this invention 
have the general formula 
##STR4## 
in which R is as defined herein and Z is a chain which contains 2 or 3 
ring atoms, at least one of which is nitrogen, oxygen or sulfur. Nitrogen 
atoms in such rings may be unsubstituted or may be substituted by a 
C.sub.1 -C.sub.4 alkyl group. Carbon atoms in such rings may be 
unsubstituted or may be substituted similarly to those in the carbocyclic 
compounds described above. Where possible, heterocyclic rings may be 
saturated or unsaturated. 
Examples of heterocyclic 1,3-dicarbonyl structures include, for instance, 
barbituric acid derivatives, hydroxypyrones, 3,5-dioxotetrahydropyrans and 
thiopyrans, cyclical oxolactones, cyclical oxothiolactones and oxalactams. 
One particular class of herbicide compounds is that in which the dicarbonyl 
compound is an optionally sustituted cyclohexanedione and the acylating 
group is a substituted benzoyl moiety. That is, R in Formula B above is 
substituted phenyl. In general, these compounds have the formula 
##STR5## 
in which 
R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are independently 
hydrogen or C.sub.1 -C.sub.4 alkyl or 
R.sup.1 or R.sup.3 is 
##STR6## 
in which R.sub.a is C.sub.1 -C.sub.4 alkyl; phenyl, optionally substituted 
by from 2 to 5 methyl groups; 
or in which R.sup.1 and R.sup.2, or R.sup.3 and R.sup.4, taken together are 
C.sub.2 -C.sub.5 alkylene (such compounds have a spiro structure); 
R.sup.7 is halogen (chlorine, bromine, iodine or fluorine); cyano; C.sub.1 
-C.sub.4 alkyl; C.sub.1 -C.sub.4 haloalkyl; R.sub.k SO.sub.n in which 
R.sub.k is C.sub.1 -C.sub.4 alkyl and n=0, 1 or 2; C.sub.1 -C.sub.4 
alkoxy; or nitro; 
R.sup.8, R.sup.9 and R.sup.10 independently are hydrogen or substituents 
including halogen; C.sub.1 -C.sub.4 alkyl; C.sub.1 -C.sub.4 alkoxy, 
trifluoromethoxy; cyano; nitro; C.sub.1 -C.sub.4 haloalkyl; C.sub.1 
-C.sub.4 alkylthio; phenoxy; or substituted phenoxy in which the 
substituent is halogen or halomethyl or both; 
R.sub.b S(O).sub.n in which n is 0, 1 or 2; and R.sub.b is C.sub.1 -C.sub.4 
alkyl, C.sub.1 -C.sub.4 haloalkyl, phenyl or benzyl, 
##STR7## 
in which R.sub.c is C.sub.1 -C.sub.4 alkyl, --NR.sub.d R.sub.e in which 
R.sub.d and R.sub.e independently are hydrogen or C.sub.1 -C.sub.4 alkyl; 
R.sub.f C(O)-- in which R.sub.f is hydrogen, C.sub.1 -C.sub.4 alkyl, 
C.sub.1 -C.sub.4 haloalkyl or C.sub.1 -C.sub.4 alkoxy; 
SO.sub.2 NR.sub.g R.sub.h in which R.sub.g and R.sub.h independently are 
hydrogen or C.sub.1 -C.sub.4 alkyl; 
or R.sup.8 and R.sup.9 taken together form a ring structure with two 
adjacant carbon atoms of the phenyl ring to which they are attached. 
Compounds of this type, with various substituents on either or both of the 
cyclohexane or phenyl rings are disclosed in: European Patent Application, 
Publication No. 90262; the following copending United States patent 
applications, assigned to the Assignee herewith, and entitled "Certain 
2-(2-Substituted Benzoyl)-1,3-Cyclohexanediones", Ser. No. 634,408, filed 
July 31, 1984; Ser. No. 640,791, filed Aug. 17, 1984; Ser. No. 752,702, 
filed July 8, 1985; and Ser. No. 722,593, filed Sept. 5, 1985; the 
following U.S. patent applications assigned to the Assignee hereof, Ser. 
No. 683,900, filed Dec. 20, 1984 and Ser. No. 802,135, filed Nov. 29, 
1985, entitled "Certain 2-(2 Nitrobenzoyl)-1,3-Cyclohexanediones"; Ser. 
No. 683,899, filed Dec. 20, 1984, entitled "Certain 
2-(2'-Cyanobenzoyl)-1,3-Cyclohexanediones"; Ser. No. 683,898, filed Dec. 
20, 1984 and Ser. No. 802,133, filed Nov. 29, 1985, entitled "Certain 
2-(2'-Substituted Benzoyl)- 1,3-Cyclohexanediones"; Ser. No. 683,884, 
filed Dec. 20, 1984 and Ser. No. 802,134, filed Nov. 29, 1985, entitled 
"Certain 2-(2'-Alkylbenzoyl)-1,3-Cyclohexanediones". The disclosures of 
these documents are hereby incorporated herein. 
Some specific types of such acylated heterocyclic 1,3-dicarbonyl herbicide 
compounds include: 
barbituric acid derivatives such as those of the formula IV 
##STR8## 
in which R.sup.18 and R.sup.19 are hydrogen or C.sub.1 -C.sub.4 alkyl and 
R is substituted phenyl such as 
##STR9## 
in which R.sup.15, R.sup.16 and R.sup.17 are as defined hereinafter. Such 
compounds are described, for instance, in copending, commonly assigned 
U.S. patent application No. 872,068, filed June 9, 1986; entitled "Certain 
S-(2-Substituted Benzoyl)-Barbituric Acids", the disclosure of which is 
hereby incorporated herein; 
oxolactams such as those having the formula V 
##STR10## 
in which R.sup.11 -R.sup.14 and R.sup.20 are independently hydrogen or 
C.sub.1 -C.sub.4 alkyl, or R.sup.11 and R.sup.12 together are C.sub.2 
-C.sub.5 alkylene, t is 0 or 1 and R is substituted phenyl such as 
##STR11## 
in which R.sup.15 is hydrogen; halogen; C.sub.1 -C.sub.2 alkyl; C.sub.1 
-C.sub.2 alkoxy; nitro; cyano; C.sub.1 -C.sub.2 haloalkyl; or R.sub.m 
SO.sub.n wherein R.sub.m is C.sub.1 -C.sub.2 alkyl and n is 0, 1 or 2; 
trifluoromethyl or difluoromethyl; or trifluoromethoxy or difluoromethoxy. 
Preferably R.sup.15 is chlorine, bromine, C.sub.1 -C.sub.2 alkyl, C.sub.1 
-C.sub.2 alkoxy, trifluoromethyl, cyano, nitro, C.sub.1 -C.sub.2 alkyl, 
C.sub.1 -C.sub.2 alkoxy, trifluoromethyl, cyano, nitro, C.sub.1 -C.sub.2 
alkylthio or C.sub.1 -C.sub.2 alkylsulfonyl; and R.sup.16 and R.sup.17 
independently are (1) hydrogen, (2) halogen; (3) C.sub.1 -C.sub.4 alkyl; 
(4) C.sub.1 -C.sub.4 alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; 
(8) C.sub.1 -C.sub.4 alkyl; (9) R.sup.b SO.sub.n -- wherein n is the 
integer 0, 1 or 2; and R.sup.b is (a) C.sub.1 -C.sub.4 alkyl; (b) C.sub.1 
-C.sub.4 alkyl substituted with halogen or cyano; (c) phenyl; or (d) 
benzyl. Such compounds are disclosed, for instance, in copending, commonly 
assigned U.S. application No. 871,973, filed June 9, 1986, entitled 
"Certain 3-(Benzoyl-4-Oxolactams" the disclosure of which is hereby 
incorporated by reference; 
Herbicidal oxolactones and oxothiolactones within this invention such as 
those having the formula VI 
##STR12## 
in which R.sup.21 -R.sup.24 are independently hydrogen or C.sub.1 -C.sub.4 
alkyl; or R.sub.21 and R.sup.22 together are C.sub.2 -C.sub.5 alkylene; or 
R.sup.23 and R.sup.24 together are C.sub.2 -C.sub.5 alkylene; or R.sup.21 
and R.sup.23 together form a bond, and R is substituted phenyl such as 
##STR13## 
in which R.sup.15 -R.sup.17 are as defined above; and W is oxygen or 
sulfur. When R.sup.21 and R.sup.23 together form a bond, the compounds 
contain an unsaturated heterocyclic ring. Such compounds are disclosed, 
for instance, in copending commonly assigned U.S. application No. 871,975, 
filed June 9, 1986; entitled "Certain 4-Oxo-Benzoyl-Valerolactones and 
Thiolactones", the disclosure of which is hereby incorporated herewith; 
dioxotetrahydropyrans and -thiopyrans such as those having the formula VII 
##STR14## 
in which R.sup.26 -R.sup.29 are independently hydrogen or C.sub.1 -C.sub.4 
alkyl or R.sup.26 and R.sup.27 together are C.sub.2 -C.sub.5 alkylene, or 
R.sup.28 and R.sup.29 together are C.sub.2 -C.sub.5 alkylene; W.sup.2 is 
oxygen, sulfur or sulfonyl and R.sup.30 is substituted phenyl such as 
##STR15## 
in which R.sup.15 -R.sup.17 are as previously defined. Such compounds are 
described, for instance, in copending, commonly assigned U.S. application 
Ser. No. 872,080, filed Sept. 9, 1986, entitled "Certain Substituted 
4-Benzoyl-3,5-Oxo-tetrahydropyrans and Thiopyrans". 
Another embodiment of this invention is an herbicidal composition 
comprising a 2-(2-substituted benzoyl)-4-(substituted or unsubstituted 
phenyl) cyclohexanedione and an antidote with an inert carrier therefor. 
The 1,3-cyclohexanedione moiety is preferably substituted with groups 
hereinafter defined. The benzoyl and cyclohexanedione moieties can be 
further substituted. 
Within the scope of this embodiment are compounds in which R in Formula B 
above is a substituted phenyl. In general, these compounds have the 
formula VIII: 
##STR16## 
wherein R.sup.140 is halogen; C.sub.1 -C.sub.2 alkyl; C.sub.1 -C.sub.2 
alkoxy; trifluoromethoxy; or difluoromethoxy; nitro; cyano; C.sub.1 
-C.sub.2 haloalkyl; R.sup.a SO.sub.n -- wherein n is 0 or 2; and R.sup.a 
is C.sub.1 -C.sub.2 alkyl; trifluoromethyl or difluoromethyl. Of 
particular interest are compounds in which R.sup.140 is chlorine, bromine, 
C.sub.1 -C.sub.2 alkyl, C.sub.1 -C.sub.2 alkoxy, trifluoromethyl, cyano, 
nitro, C.sub.1 -C.sub.2 alkylthio or C.sub.1 -C.sub.2 alkylsulfonyl; more 
preferably chlorine, nitro, methyl, trifluormethyl or methylsulfonyl; and 
R.sup.131 is hydrogen or C.sub.1 -C.sub.4 alkyl; 
R.sup.132 is hydrogen or C.sub.1 -C.sub.4 alkyl; 
R.sup.131 and R.sup.132 together are C.sub.2 -C.sub.5 alkylene; 
R.sup.133 is hydrogen or C.sub.1 -C.sub.4 alkyl; 
R.sup.134 is hydrogen or C.sub.1 -C.sub.4 alkyl; 
R.sup.133 and R.sup.134 together are C.sub.2 -C.sub.5 alkylene; 
R.sup.135, R.sup.136, R.sup.137 and R.sup.138 independently are (1) 
hydrogen; (2) chlorine, fluorine or bromine; (3) C.sub.1 -C.sub.4 alkyl; 
(4) C.sub.1 -C.sub.4 alkoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; 
(8) C.sub.1 -C.sub.4 haloalkyl; (9) R.sup.b SO.sub.n -- wherein n is the 
integer 0, 1 or 2; and 
R.sup.b is (a) C.sub.1 -C.sub.4 alkyl; 
(b) C.sub.1 -C.sub.4 alkyl substituted with halogen or cyano; 
(c) phenyl; or 
(d) benzyl; 
(10) --NR.sup.c R.sup.d wherein 
R.sup.c and R.sup.d independently are hydrogen or C.sub.1 -C.sub.4 alkyl; 
(11) R.sup.e C(O)-- wherein R.sup.e is C.sub.1 -C.sub.4 alkyl or C.sub.1 
-C.sub.4 alkoxy; (12) --SO.sub.2 NR.sup.c R.sup.d wherein R.sup.c and 
R.sup.d are as defined; or (13) --N(R.sup.c)C(O)R.sup.d wherein R.sup.e 
and R.sup.d are as defined; and 
R.sup.139 is hydrogen or C.sub.1 -C.sub.4 alkyl. 
Preferably R.sup.135 is in the 3-position and R.sup.135 and R.sup.137 are 
hydrogen, chlorine, fluorine, trifluoromethyl, cyano, C.sub.1 -C.sub.4 
alkoxy or C.sub.1 -C.sub.4 thioalkyl; or R.sup.135 and R.sup.137 are 
hydrogen and R.sup.136 and R.sup.138 are in the 4-position; wherein 
R.sup.136 and R.sup.138 are halogen, cyano, trifluoromethyl, or R.sup.b 
SO.sub.2 wherein R.sup.b is C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 
haloalkyl. 
Compounds of this type are described in copending U.S. application Ser. No. 
906,462, filed Sept. 12, 1986. 
Another embodiment of this invention is an herbicidal composition 
comprising an herbicidally active 2-(substituted 
benzoyl)-cyclohexanedione-1,3 and the acylating group is a substituted 
benzoyl moiety and an antidote with an inert carrier therefor. The 4- and 
6-positions of the cyclohexanedione-1,3 moiety are preferably substituted 
with groups hereinafter defined, most preferably with hydrogen or methyl 
groups. The substituted benzoyl and cyclohexanedione-1,3 moieties can be 
further substituted. 
Within the scope of this embodiment are the compounds in which R in Formula 
B, above, is substituted phenyl. In general, these compounds have the 
formula IX: 
##STR17## 
wherein 
R.sup.50 is halogen; C.sub.1 -C.sub.2 alkyl; C.sub.1 -C.sub.2 alkoxy; 
trifluoromethoxy or difluoromethoxy; nitro; cyano; C.sub.1 -C.sub.2 
haloalkyl; R.sup.a SO.sub.n -- wherein n is 0 or 2; and R.sup.a is C.sub.1 
-C.sub.2 alkyl; trifluoromethyl; or difluoromethyl; and 
R.sup.41 is hydrogen or C.sub.1 -C.sub.4 alkyl; 
R.sup.42 is hydrogen or C.sub.1 -C.sub.4 alkyl; 
R.sup.41 and R.sup.42 together are C.sub.2 -C.sub.5 alkylene; 
R.sup.43 is hydrogen or C.sub.1 -C.sub.4 alkyl; 
R.sup.44 is hydrogen or C.sub.1 -C.sub.4 alkyl; 
R.sup.43 and R.sup.44 together are C.sub.2 -C.sub.5 alkylene; 
R.sup.45, R.sup.46, R.sup.47 and R.sup.48 independently are (1) hydrogen; 
(2) halogen selected from the group consisting of chlorine, fluorine or 
bromine; (3) C.sub.1 C.sub.4 alkyl; (4) C.sub.1 -C.sub.4 alkoxy; (5) 
trifluoromethoxy; (6) cyano; (7) nitro; (8) C.sub.1 -C.sub.4 haloalkyl; 
(9) R.sup.b SO.sub.n -- wherein n is the integer 0, 1 or 2; and 
R.sup.b is (a) C.sub.1 -C.sub.4 alkyl; 
(b) C.sub.1 -C.sub.4 alkyl substituted with halogen or cyano; 
(c) phenyl; or 
(d) benzyl; 
(10) --NR.sup.c R.sup.d wherein 
R.sup.c and R.sup.d independently are hydrogen or C.sub.1 -C.sub.4 alkyl; 
(11) R.sup.e C(O)-- wherein R.sup.e is C.sub.1 -C.sub.4 alkyl or C.sub.1 
-C.sub.4 alkoxy; (12) --SO.sub.2 NR.sup.c R.sup.d wherein R.sup.c and 
R.sup.d are as defined; or (13) --N(R.sup.c)C(O)R.sup.d wherein R.sup.e 
and R.sup.d are as defined; and 
R.sup.49 is hydrogen or C.sub.1 -C.sub.4 alkyl. 
Of particular interest are compounds in which R.sup.45 is in the 3-position 
and R.sup.45 is hydrogen, chlorine, fluorine, trifluoromethyl, cyano, 
C.sub.1 -C.sub.4 alkoxy or C.sub.1 -C.sub.4 thioalkyl; or R.sup.45 is 
hydrogen; or R.sup.46 is in the 4-position; and R.sup.46 is halogen, 
cyano, trifluoromethyl, or R.sup.b SO.sub.2 wherein R.sup.b is C.sub.1 
-C.sub.4 alkyl, preferably methyl or C.sub.1 -C.sub.4 haloalkyl, 
difluoromethyl or trifluoromethyl. 
Compounds of this type are described in copending U.S. patent application 
Ser. No. 906,461, filed Sept. 12, 1986. 
Another embodiment of this invention is an herbicidal composition 
comprising an herbicidally active 2-(2-substituted benzoyl)-4-(substituted 
oxy or substituted thio)-1,3-cyclohexanedione and an antidote with an 
inert carrier therefor. The 5- and 6-positions of the 1,3-cyclohexanedione 
moiety are preferably substituted with groups hereinafter defined, most 
preferably with hydrogen or methyl groups. The substituted benzoyl and 
cyclohexanedione moieties can be further substituted. 
Within the scope of this embodiment are compounds having the following 
structural formula 
##STR18## 
wherein 
X is oxy, thio, sulfinyl or sulfonyl; 
R.sup.50 is halogen; C.sub.1 -C.sub.2 alkyl; C.sub.1 -C.sub.2 alkoxy, 
preferably methoxy; trifluoromethoxy; difluoromethoxy; nitro; cyano; 
C.sub.1 -C.sub.2 haloalkyl; R.sup.a SO.sub.n -- wherein n is 0 or 2, 
preferably 2 and R.sup.a is C.sub.1 -C.sub.2 alkyl; trifluoromethyl or 
difluoromethyl. Preferably, R.sup.50 is chlorine, bromine, C.sub.1 
-C.sub.2 alkyl, C.sub.1 -C.sub.2 alkoxy, trifluoromethyl, cyano, nitro, 
C.sub.1 -C.sub.2 alkylthio or C.sub.1 -C.sub.2 alkylsulfonyl; more 
preferably chlorine, nitro, methyl, trifluoromethyl or methylsulfonyl; 
R.sup.51 is hydrogen; C.sub.1 -C.sub.4 alkyl; phenyl; or substituted 
phenyl; 
R.sup.52 is hydrogen or C.sub.1 -C.sub.4 alkyl; or 
R.sup.51 and R.sup.52 together are C.sub.2 -C.sub.5 alkylene; 
R.sup.53 is hydrogen; C.sub.1 -C.sub.4 alkyl; phenyl; or substituted phenyl 
with the proviso that R.sup.51 and R.sup.53 are not both phenyl or 
substituted phenyl; 
R.sup.54 is hydrogen or C.sub.1 -C.sub.4 alkyl; 
R.sup.55 is hydrogen or C.sub.1 -C.sub.4 alkyl; 
R.sup.56 is hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, 
or phenyl and 
R.sup.57 and R.sup.58 independently are (1) hydrogen; (2) halogen; (3) 
C.sub.1 -C.sub.4 alkyl; (4) C.sub.1 -C.sub.4 alkoxy; (5) trifluoromethoxy; 
(6) cyano; (7) nitro; 
(8) C.sub.1 -C.sub.4 haloalkyl; (9) R.sup.b SO.sub.n -- wherein n is the 
integer 0, 1 or 2; and 
R.sup.b is (a) C.sub.1 -C.sub.4 alkyl; 
(b) C.sub.1 -C.sub.4 alkyl substituted with halogen or cyano; 
(c) phenyl; or 
(d) benzyl; 
(10) --NR.sup.c R.sup.d wherein 
R.sup.c and R.sup.d independently are hydrogen or C.sub.1 -C.sub.4 alkyl; 
(11) R.sup.e C(O)-- wherein R.sup.e is C.sub.1 -C.sub.4 alkyl or C.sub.1 
-C.sub.4 alkoxy; (12) --SO.sub.2 NR.sup.c R.sup.d wherein R.sup.c and 
R.sup.d are as defined; or (13) --N(R.sup.c)C(O)R.sup.d wherein R.sup.c 
and R.sup.d are as defined. 
Compounds of this type are described in copending U.S. patent application 
Ser. No. 919,280, filed Oct, 16, 1986. 
Another embodiment of this invention is an herbicidal composition 
comprising an herbicidally active 2-(2-substituted benzoyl)-4-(substituted 
imino, oximino or carbonyl)-1,3-cyclohexanedione and an antidote with an 
inert carrier therefor. The 5- and 6-positions of the 1,3-cyclohexanedione 
moiety are substituted with groups hereinafter defined, preferably with 
hydrogen or methyl groups. The benzoyl and imino, oximino or carbonyl 
moieties can be substituted. 
Also embodied within the scope of this invention are novel compounds having 
the following structural formula 
##STR19## 
wherein 
X is oxygen or NR.sup.69 wherein R.sup.69 is hydrogen, C.sub.1 -C.sub.4 
alkyl, or C.sub.1 -C.sub.4 alkoxy; 
R.sup.60 is halogen; C.sub.1 -C.sub.2 alkyl; C.sub.1 -C.sub.2 alkoxy; 
trifluoromethoxy or difluoromethoxy; nitro; cyano; C.sub.1 -C.sub.2 
haloalkyl; R.sup.a SO.sub.n -- wherein n is 0 or 2; and R.sup.a is C.sub.1 
-C.sub.2 alkyl; trifluoromethyl; or difluoromethyl. Preferably, R.sup.60 
is chlorine, bromine, C.sub.1 -C.sub.2 alkyl, C.sub.1 -C.sub.2 alkoxy, 
trifluorometyl, cyano, nitro, C.sub.1 -C.sub.2 alkylthio or C.sub.1 
-C.sub.2 alkylsulfonyl; more preferably chlorine, nitro, methyl, 
trifluoromethyl or methylsulfonyl; and 
R.sup.61 is hydrogen; C.sub.1 -C.sub.4 alkyl; phenyl; or substituted 
phenyl; 
R.sup.62 is hydrogen or C.sub.1 -C.sub.4 alkyl; or 
R.sup.61 and R.sup.62 together are C.sub.2 -C.sub.5 alkylene; 
R.sup.63 is hydrogen; C.sub.1 -C.sub.4 alkyl; phenyl; or substituted 
phenyl, with the proviso that R.sup.61 and R.sup.63 are not both phenyl or 
substituted phenyl; 
R.sup.64 is hydrogen or C.sub.1 -C.sub.4 alkyl; 
R.sup.65 is hydrogen or C.sub.1 C.sub.4 alkyl: 
R.sup.66 is C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 haloalkyl; 
R.sup.67 and R.sup.68 independently are (1) hydrogen; (2) halogen; (3) 
C.sub.1 -C.sub.4 alkyl; (4) C.sub.1 -C.sub.4 alkoxy; (5) trifluoromethoxy; 
(6) cyano; (7) nitro; (8) C.sub.1 -C.sub.4 haloalkyl, preferably 
trifluoromethyl; (9) R.sup.b SO.sub.n -- wherein n is the integer 0, 1 or 
2, preferably 2; and 
R.sup.b is (a) C.sub.1 -C.sub.4 alkyl; 
(b) C.sub.1 -C.sub.4 alkyl substituted with halogen or cyano; 
(c) phenyl; or 
(d) benzyl; 
(10) --NR.sup.c R.sup.d wherein 
R.sup.c and R.sup.d independently are hydrogen or C.sub.1 -C.sub.4 alkyl; 
(11) R.sup.e C(O)-- wherein R.sup.e is C.sub.1 -C.sub.4 alkyl or C.sub.1 
-C.sub.4 alkoxy; (12) SO.sub.2 NR.sup.c R.sup.d wherein R.sup.c and 
R.sup.d are as defined; or (13) --N(R.sup.c)C(O)R.sup.d wherein R.sup.c 
and R.sup.d are as defined. 
Within this embodiment, preferably R.sup.67 is in the 3-position and 
R.sup.67 is hydrogen, chlorine, fluorine, trifluoromethyl, cyano, C.sub.1 
-C.sub.4 alkoxy or C.sub.1 -C.sub.4 thioalkyl; and preferably R.sup.68 is 
in the 4-position and R.sup.68 is halogen, cyano, trifluoromethyl, or 
R.sup.b SO.sub.2 wherein R.sup.b is C.sub.1 -C.sub.4 alkyl, or C.sub.1 
haloalkyl, preferably chloromethyl, difluoromethyl or trifluoromethyl. 
Compounds of this type are described in copending U.S. patent application 
Ser. No. 919,278, filed Oct. 16, 1986. 
Another embodiment of this invention is an herbicidal composition 
comprising an herbicidally active 2-(2-substituted 
benzoyl)-4-(substituted)-1,3-cyclohexanedione and an antidote with an 
inert carrier therefor. The 5- and 6-positions and the 4-position of the 
1,3-cyclohexanedione moiety are preferably substituted with groups 
hereinafter defined, most preferably with halogen or methyl groups. The 
benzoyl moiety can be substituted, with the groups as hereinafter recited. 
Within the scope of this embodiment are compounds having the following 
structural formula 
##STR20## 
wherein 
R.sup.70 is halogen; C.sub.1 -C.sub.2 alkyl; C.sub.1 -C.sub.2 alkoxy; 
trifluoromethoxy; diflouromethoxy; nitro; cyano; C.sub.1 -C.sub.2 
haloalkyl; R.sup.a SO.sub.n -- wherein n is 0 or 2; and R.sup.a is C.sub.1 
-C.sub.2 alkyl; trifluoromethyl or difluoromethyl. Preferably, R.sup.70 is 
chlorine, bromine, C.sub.1 -C.sub.2 alkyl, C.sub.1 -C.sub.2 alkoxy, 
trifluoromethyl, cyano, nitro, C.sub.1 -C.sub.2 alkylthio or C.sub.1 
-C.sub.2 alkylsulfonyl; more preferably chlorine, nitro, methyl, 
trifluoromethyl or methylsulfonyl; and 
R.sup.71 is hydrogen; C.sub.1 -C.sub.4 alkyl; halogen; phenyl; or 
substituted phenyl; 
R.sup.72 is hydrogen or C.sub.1 -C.sub.4 alkyl; or 
R.sup.71 and R.sup.72 together are C.sub.2 -C.sub.5 alkylene; 
R.sup.73 is hydrogen; C.sub.1 -C.sub.4 alkyl; phenyl; or substituted 
phenyl, with the proviso that R.sup.71 and R.sup.73 are not both phenyl or 
substituted phenyl; 
R.sup.74 is hydrogen or C.sub.1 -C.sub.4 alkyl; 
R.sup.75 is hydrogen, halogen or C.sub.1 -C.sub.4 alkyl; 
R.sup.76 is halogen, nitro, cyano, trifluoromethyl; --C(O)NR.sub.2.sup.b 
wherein R.sup.b is hydrogen or C.sub.1 -C.sub.2 alkyl; and 
R.sup.77 and R.sup.78 independently are (1) hydrogen; (2) halogen; (3) 
C.sub.1 -C.sub.4 alkyl; (4) C.sub.1 -C.sub.4 alkoxy; (5) trifluoromethoxy; 
(6) cyano; (7) nitro; (8) C.sub.1 -C.sub.4 haloalkyl; (9) R.sup.b SO.sub.n 
-- wherein n is the integer 0, 1 or 2; and 
R.sup.b is (a) C.sub.1 -C.sub.4 alkyl; 
(b) C.sub.1 -C.sub.4 alkyl substituted with halogen or cyano; 
(c) phenyl; or 
(d) benzyl; 
(10) --NR.sup.c R.sup.d wherein 
R.sup.c and R.sup.d independently are hydrogen or C.sub.1 -C.sub.4 alkyl; 
(11) R.sup.e C(O)-- wherein R.sup.e is C.sub.1 -C.sub.4 alkyl or C.sub.1 
-C.sub.4 alkoxy; (12) --SO.sub.2 NR.sup.c R.sup.d wherein R.sup.c and 
R.sup.d are as defined; or (13) --N(R.sup.c)C(O)R.sup.d wherein R.sup.c 
and R.sup.d are as defined. 
Within this embodiment, preferably R.sup.77 is in the 3-position and 
R.sup.77 is hydrogen, chlorine, fluorine, trifluoromethyl, cyano, C.sub.1 
-C.sub.4 alkoxy or C.sub.1 C.sub.4 thioalkyl; preferably R.sup.78 is in 
the 4-position and R.sup.78 is halogen, cyano, trifluoromethyl, or R.sup.b 
SO.sub.2 wherein R.sup.b is C.sub.1 -C.sub.4 alkyl, or C.sub.1 -C.sub.4 
haloalkyl, preferably chloromethyl, difluoromethyl or trifluoromethyl. 
Compounds of this type are described in copending U.S. patent application 
Ser. No. 919,277, filed Oct. 16, 1986. 
The term "C.sub.1 -C.sub.4 alkyl" includes methyl, ethyl, n-propyl, 
isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl. The term "halogen" 
includes chlorine, bromine, iodine and fluorine. The terms "C.sub.1 
-C.sub.4 alkoxy" includes methoxy, ethoxy, n-propoxy, isopropoxy, 
n-butoxy, sec-butoxy, isobutoxy and t-butoxy. The term "C.sub.1 -C.sub.4 
haloalkyl" includes the alkyl groups defined above under C.sub.1 -C.sub.4 
alkyl in which on or more hydrogens is replaced by chlorine, bromine, 
iodine or fluorine. 
Salts of the above-described compounds are included within the scope of the 
instant invention. 
One method for production of acylated dicarbonyl compounds is disclosed in 
European Patent Application, Publication No. 186,117. 
The following is a list of sample compounds as found in the above 
description of active herbicides. 
__________________________________________________________________________ 
##STR21## 
Cmpd. 
No. R3 R.sup.4 
R.sup.7 
R.sup.8 
R.sup.9 R.sup.10 
__________________________________________________________________________ 
51A H H Cl H 4-CH.sub.3 SO.sub.2 
H 
55A CH.sub.3 
CH.sub.3 
Cl H 4-CH.sub.3 SO.sub.2 
H 
90A H H Cl 3-C.sub.2 H.sub.5 O 
4-C.sub.2 H.sub.5 SO.sub.2 
H 
__________________________________________________________________________ 
##STR22## 
Comp. 
No. R.sup.1 
R.sup.2 
R.sup.3 
R.sup.4 
R.sup.5 
R.sup.6 
R.sup.8 
R.sup.9 
__________________________________________________________________________ 
1C CH.sub.3 
CH.sub.3 
H H H H H H 
__________________________________________________________________________ 
##STR23## 
Comp. 
No. R.sup.1 
R.sup.2 
R.sup.3 
R.sup.4 
R.sup.5 
R.sup.6 
R.sup.8 
R.sup.9 
__________________________________________________________________________ 
4D CH.sub.3 
CH.sub.3 
H H H H H H 
8D H H H H H H H CF.sub.3 
24D CH.sub.3 
CH.sub.3 
H H H H H SO.sub.2 CH.sub.3 
70D H H H H CH.sub.3 
CH.sub.3 
H SO.sub.2 CH.sub.2 Cl 
__________________________________________________________________________ 
##STR24## 
Comp. 
No. n R.sup.K 
R.sup.1 
R.sup.2 
R.sup.3 
R.sup.4 
R.sup.5 
R.sup.6 
R.sup.8 
R.sup.9 
__________________________________________________________________________ 
4E 2 CH.sub.3 
CH.sub.3 
CH.sub.3 
H H CH.sub.3 
H H H 
16E 0 CH.sub.3 
H H H H H H H SO.sub.2 n-C.sub.3 H.sub.7 
__________________________________________________________________________ 
##STR25## 
Comp. 
No. R.sup.50 
R.sup.51 
R.sup.52 
R.sup.53 
R.sup.54 
R.sup.55 
R.sup.56 
R.sup.57 
R.sup.58 
__________________________________________________________________________ 
8F CH.sub.3 
CH.sub.3 
CH.sub.3 
H H CH.sub.3 
H H CH.sub.3 SO.sub.2 
29F CF.sub.3 
H H H H H H H C.sub.2 H.sub.5 S 
36F CH.sub.3 
H H H H H H 3-Cl 
C.sub.2 H.sub.5 SO.sub.2 
50F CF.sub.3 
CH.sub.3 
CH.sub.3 
H H H H H CF.sub.3 
__________________________________________________________________________ 
##STR26## 
Cmpd. 
No. R.sup.140 
R.sup.131 
R.sup.132 
R.sup.133 
R.sup.134 
R.sup.135 
R.sup.136 
R.sup.137 
R.sup.138 
R.sup.139 
__________________________________________________________________________ 
VIII-14 
Cl H H Me H H 4-SO.sub.2 Me 
2-F 
H H 
VIII-17 
NO.sub.2 
H H H H H 4-Cl 2-F 
H Me 
VIII-24 
Cl H H H H H 4-SO.sub.2 Me 
H H H 
__________________________________________________________________________ 
##STR27## 
Comp. 
No. R.sup.50 
R.sup.41 
R.sup.42 
R.sup.43 
R.sup.44 
R.sup.45 
R.sup.46 
R.sup.47 
R.sup.48 
R.sup.49 
__________________________________________________________________________ 
II-4 
Cl CH.sub.3 
CH.sub.3 
H H H 4-SO.sub.2 CH.sub.3 
H H H 
II-6 
NO.sub.2 
H H H H H 4-Cl H H H 
__________________________________________________________________________ 
##STR28## 
Cmpd. 
No. R.sup.15 
R.sup.26 
R.sup.27 
R.sup.28 
R.sup.29 
R.sup.16 
R.sup.17 
W.sup.2 
__________________________________________________________________________ 
VII-1 
NO.sub.2 
CH.sub.3 
CH.sub.3 
H H H 4-Cl 
O 
VII-5 
Cl H H H H H 4-Cl 
S 
VII-7 
Cl CH.sub.3 
H CH.sub.3 
H H 4-Cl 
S 
__________________________________________________________________________ 
##STR29## 
Comp. 
No. R.sup.15 
R.sup.21 
R.sup.22 
R.sup.23 
R.sup.24 
R.sup.16 
R.sup.17 
W 
__________________________________________________________________________ 
VI-1 Cl H CH.sub.3 
bond H 4-Cl O 
VI-4 NO.sub.2 
H CH.sub.3 
H H H H O 
VI-9 NO.sub.2 
H CH.sub.3 
H CH.sub.3 
H 4-Cl O 
VI-21 
Cl H CH.sub.3 
H CH.sub.3 
H 4-SO.sub.2 CH.sub.3 
S 
__________________________________________________________________________ 
##STR30## 
Cmpd. No. 
R.sup.15 
R.sup.18 
R.sup.19 
R.sup.16 
R.sup.17 
__________________________________________________________________________ 
IV-1 Cl CH.sub.3 
CH.sub.3 
H 4-Cl 
IV-6 NO.sub.2 
CH.sub.3 
CH.sub.3 
H H 
__________________________________________________________________________ 
##STR31## 
Comp. 
No. R.sup.15 
R.sup.11 
R.sup.12 
R.sup.13 
R.sup.14 
R.sup.16 
R.sup.17 
R.sup.20 
t 
__________________________________________________________________________ 
V-1 NO.sub.2 
H H H H H 4-Cl n-C.sub.3 H.sub.7 
1 
V-2 NO.sub.2 
H H n/a n/a H 4-Cl n-C.sub.3 H.sub.7 
0 
V-3 Cl H H H H H 4-SO.sub.2 CH.sub.3 
n-C.sub.3 H.sub.7 
1 
V-7 NO.sub.2 
H H CH.sub.3 
CH.sub.3 
H 4-Cl CH.sub.3 
1 
V-15 
NO.sub.2 
CH.sub.3 
H H H H 4-SO.sub.2 CH.sub.3 
C.sub.2 H.sub.5 
1 
__________________________________________________________________________ 
##STR32## 
Comp. 
No. R.sup.59 
R.sup.51 
R.sup.52 
R.sup.53 
R.sup.54 
R.sup.55 
X R.sup.56 
R.sup.57 
R.sup.58 
__________________________________________________________________________ 
X-5 Cl H H H H H S CH.sub.3 
H 4-SO.sub.2 CH.sub.3 
X-6 NO.sub.2 
H H H H H SO.sub.2 
CH.sub.3 
H 4-Cl 
X-13 
NO.sub.2 
H H H H CH.sub.3 
S CH.sub.3 
H H 
__________________________________________________________________________ 
##STR33## 
Cmpd. 
No. R.sup.60 
R.sup.61 
R.sup.62 
R.sup.63 
R.sup.64 
R.sup.65 
R.sup.66 
R.sup.67 
R.sup.68 
X 
__________________________________________________________________________ 
XI-1 
Cl H H H H H CH.sub.3 
H 4-SO.sub.2 CH.sub.3 
C.sub.2 H.sub.5ON 
XI-6 
Cl H H H H H CH.sub.3 
3-Cl 
4-SO.sub.2 C.sub.2 H.sub.5 
CH.sub.3ON 
XI-7 
NO.sub.2 
H H H H H CH.sub.3 
H 4-Cl CH.sub.3ON 
XI-8 
Cl H H H H H CF.sub.3 
H 4-Cl CH.sub.3ON 
__________________________________________________________________________ 
##STR34## 
Cmpd. 
No. R.sup.70 
R.sup.71 
R.sup.72 
R.sup.73 
R.sup.74 
R.sup.75 
R.sup.76 
R.sup.77 
R.sup.78 
__________________________________________________________________________ 
XII-1 
Cl H H H H H Br H 4-SO.sub.2 CH.sub.3 
XII-6 
NO.sub.2 
CH.sub.3 
CH.sub.3 
H H H Br H H 
XII-7 
Cl H H H H H Cl H 4-Cl 
XII-9 
NO.sub.2 
H H CH.sub.3 
CH H F H 4-CF.sub.3 
__________________________________________________________________________ 
DESCRIPTION OF ANTIDOTES 
The phenoxyalkanoic acids are the best known and most widely available of 
this class of compound. Normally, they are widely used for their selective 
weed killing properties, but sublethal doses are used as growth regulators 
to promote fruit set and for thinning. The most notable of the class are 
2,4-dichlorophenoxy acetic acid (2,4-D), its esters, amides and salts; 
2,4,5-trichlorophenoxy acetic acid (2,4,5-T), its esters, amides and 
salts; and (4-chloro-o-tolyloxy)acetic acid (4-CPA). Further examples of 
the various salts and esters are: sodium salt, potassium salt, ammonium 
salt, triethylamine salt, triethanolamine salt, the alkyl ester, such as 
butyl ester, butoxyethanol ester, propyleneglycolbutylether ester, and 
tetrahydrofurfuryl ester. Also of interest, in place of the phenoxy acetic 
acid portion or grouping the alpha- and beta-phenoxyproprionic acid, 
alpha- and beta-phenoxybutyric acid, or higher analog may be substituted. 
The chlorophenoxy compounds described above have profound effects upon the 
growth and structure of plants when used in an herbicidally effective 
amount. Various disruptions such as epinastic bending, formation of 
tumors, cessation in the division of the meristematic cells, elongating 
cells stop length growth but continue radial expansion, phytosynthesis is 
inhibited and other hormonal imbalanced effects caused by the herbicide, 
the imbalance could be in the auxin-kinin relation. 
This invention embodies a two-part herbicidal system comprised of (a) an 
herbicide as described hereinabove and (b) an effective antidote therefor. 
It has been found that such preferred antidote compounds within the 
instant invention are selected from the general class of chemical 
substances known and described above as aryloxyalkanoic acids and their 
derivatives, which have been found to be effective as herbicide antidotes 
for the above-described acylated 1,3-dicarbonyl herbicides. The preferred 
compositions of this invention may include any one or more of such 
antidotes with the described herbicides. The variety of crops on which the 
above-described herbicides is useful can be significantly broadened by the 
use of an antidote to protect one or more crops from injury therefrom and 
render the composition more selective against weeds. Some of the preferred 
antidotes are the di- and tri-halophenoxyalkanoic acids and esters, amides 
and salts thereof. 
Phenoxyalkanoic compounds of this type are described in a number of 
publications such as Ashton and Crafts, Mode of Action of Herbicides, 2nd 
Ed., Wiley and Sons, pp. 272-302 (1981). 
According to this invention, the phenoxy acids can have the following 
general formula with varied substituent definitions: 
##STR35## 
wherein 
x is an integer from 0 to 6, inclusive; 
M, N and P are selected from the group consisting of hydrogen, halogen and 
lower alkyl having 1 to 4 carbon atoms, inclusive; 
R.sub.1 and R.sub.2 are hydrogen or lower alkyl having 1 to 4 carbon atoms, 
inclusive; 
X is oxygen or sulfur; and 
R.sub.3 is selected from the group -XR.sub.4, 
##STR36## 
hydrogen, alkyl having from 1 to 6 carbon atoms, inclusive, aryl, aralkyl, 
alkoxyalkyl, alkylthioalkyl, alkylaminoalkyl, aryloxylakyl; 
R.sub.4 and R.sub.5 are independnetly selected from the group consisting of 
hydrogen, alkyl having 1 to 6 carbon atoms, inclusive, aryl, aralkyl, 
alkoxyalkyl, alkylthioalkyl, alkylaminoalkyl, aryloxyalkyl; 
R.sub.3, R.sub.4 and R.sub.5 are independently selected from the group 
consisting of haloalkyl, alkenyl, haloalkenyl, alkylaryl, aryloxyalkyl, 
heterocyclicalkyl, cycloalkyl, furfuryl, tetrahydrofurfuryl, hydroxy, and 
--NHOH; 
R.sub.4 and R.sub.5 taken together with the nitrogen can form a 
heterocyclic ring having from 2 to 6 carbon atoms, inclusive, quinoline 
and isoquinoline. 
Preferably, the alkanoic acid portion has from about 2 to about carbon 
atoms, inclusive. Examples of suitable phenoxyalkanoic acid, salt, amide 
and ester compounds include: (2,4-dichlorophenoxy)acetic acid (2,4-D); 
(2,4,5-trichlorophenoxy)acetic acid; 4-(2,4-dichlorophenoxy)butyric acid; 
4-[(4-chloro-o-tolyl)oxy]butyric acid; 2-[(4-chloro-o-tolyl)oxy]propionic 
acid; 2-(2,4-trichlorophenoxy)propionic acid; 
2-(2,4dichlorophenoxy)propionic acid; dimethylamine salt of 
3,6-dichloro-o-anisico acid (Dicamba); dimethylamine salt of 
p-chloro-o-methylphenoxyacetic acid (MCPA); di-n-butylamine salt of 
(2,4-dichlorohenoxy)acetic acid; and triethanolamine salt of 
4-amine-3,5,6-trichloropicolinic acid; but does not exclude, any other 
generically covered compounds of the type known as "phenoxys". 
Other aryloxyalkanoic or auxin-type compounds, either natural or synthetic, 
which are phytohormones and which cause extension of growth of plant cells 
include, for example, indole acetic acid and derivatives thereof; 
4-chloroindole-3-acetic acid; phenylacetic acid; 4-[indol-3-yl]butyric 
acid; alpha-naphthylacetic acid; 2-naphthyloxyacetic acid; and 
1-naphthylacetaxide. 
The antidote is applied in conjunction with the herbicide in a 
non-phytotoxic antidotally effective amount. By "non-phytotoxic" is meant 
an amount of the antidote which causes at most minor or no injury to the 
desired crop species. By "antidotally effective" is meant an antidote used 
in an amount which is effective as an antidote with the herbicide to 
decrease the extent of injury caused by the herbicide to the desired crop 
species. The preferred weight ratio of herbicide to antidote is from about 
0.1:1 to about 30:1. Another preferred weight ratio range is from about 
1:1 to about 20:1. An even more preferred weight ratio range is from about 
2:1 to about 15:1. 
The following examples are for illustrative purposes only and are not 
intended as necessarily representative of the overall testing performed 
and are not intended to limit the invention in any way. As one skilled in 
the art is aware, in herbicidal testing, a significant number of factors 
that are not readily controllable can affect the results of individual 
tests and render them non-reproducible. For example, the results may vary 
depending on environmental factors, such as amount of sunlight and water, 
soil type, pH of the soil, temperature, and humidity, among other factors. 
Also, the depth of planting, the application rate of the herbicide, the 
application rate of the antidote, and the ratio of the 
herbicide-to-antidote application, as well as the nature of crops being 
tested, can affect the results of the test. Results may vary from crop to 
crop and within the crop varieties.

BIOLOGICAL EXAMPLES 
The ability of the aryloxyalkanoic acid derviatives to protect, safen, 
reverse or otherwise antidote the effect of acylated 1,3-dicarbonyl 
herbicides can be inferred from the following examples. 
EXAMPLE 
Test with herbicide and antidote in sugarcane. 
ANTIDOTAL EFFECT FIELD DATA 
Tests 1-4 are under field conditions. 
Phenoxy acetic acid antidote: Dimethylamine salt of 2,4-dichlorophenoxy 
acetic acid--2,4-D tank-mixed 
______________________________________ 
Test 1: Ratoon Sugarcane 
Variety: NA 5679 
Volume Application: 400 l/ha 
Method and Stage of sugarcane at application: 
POES (post-emergence surface) 
Replications: 3 
Results: 8 days after treatment (DAT) 
Rate % of Plants with 
% of the plant 
Compounds 
kg ai/ha bleaching bleached 
______________________________________ 
51A 1.0 10 5 
51A + 2,4-D 
1.0 + 2.6 10 3 
8D 0.5 43 18 
8D + 2,4-D 
0.5 + 2.16 
0 0 
24D 0.25 63 22 
24D + 2,4-D 
0.25 + 2.16 
0 0 
24D 0.5 70 30 
24D + 2,4-D 
0.5 + 2.16 
3 2 
4D 1.0 70 28 
4D + 2,4-D 
1.0 + 2.16 
3 2* 
______________________________________ 
*Only plants treated with 4D + 2,4D showed further late bleaching. 
______________________________________ 
Test 2: Ratoon Sugarcane 
Variety: NA 5679 
Volume Application: 350 l/ha 
Method and Stage of sugarcane at application: 
POES, Sugarcane 35 cm high 
Replications: 3 
Results: 8 DAT 
Rate % of Plants with 
% of the plant 
Compounds 
kg ai/ha bleaching bleached 
______________________________________ 
51A 1.0 0 0 
51A + 2,4-D 
1.0 + 2.6 0 0 
8D 0.5 100 15 
8D + 2,4-D 
0.5 + 2.16 
0 0 
24D 0.25 100 23 
24D + 2,4-D 
0.25 + 2.16 
0 0 
24D 0.5 100 32 
24D + 2,4-D 
0.5 + 2.16 
0 0 
4D 1.0 100 20 
4D + 2,4-D 
1.0 + 2.16 
0 0 
______________________________________ 
______________________________________ 
Test 3: Ratoon Sugarcane 
Variety: NA 5679 
Volume Application: 325 l/ha 
Method and Stage of sugarcane at application: 
POES, Sugarcane 26 cm high 
Replications: 3 
Results: 8 DAT 
Rate % of Plants with 
% of the plant 
Compounds 
kg ai/ha bleaching bleached 
______________________________________ 
51A 1.0 4 1 
51A + 2,4-D 
1.0 + 1.5 2 1 
51A + 2,4-D 
1.0 + 2.0 2 1 
51A - 2,4-D 
1.0 + 2.5 2 1 
8D 0.75 45 55 
8D + 2,4-D 
0.75 + 1.5 
0 0 
8D + 2,4-D 
0.75 + 2.0 
2 1 
8D + 2,4-D 
0.75 + 2.5 
0 0 
24D 0.25 100 60 
24D + 2,4-D 
0.25 + 1.5 
0 0 
24D + 2,4-D 
0.25 + 2.0 
5 1 
24D + 2,4-D 
0.25 + 2.5 
2 1 
24D 0.5 100 85 
24D + 2,4-D 
0.5 + 1.5 0 0 
24D + 2,4-D 
0.5 + 2.0 0 0 
24D + 2,4-D 
0.5 + 2.5 0 0 
4D 1.0 75 60 
4D + 2,4-D 
1.0 + 1.5 38 35 
4D + 2,4-D 
1.0 + 2.0 45 35 
4D + 2,4-D 
1.0 + 2.5 13 25 
______________________________________ 
______________________________________ 
Test 4: Newly Planted Sugarcane 
Variety: NA 5679 
Volume Application: 400 l/ha 
Method and Stage of sugarcane at application: 
POES, Sugarcane at 20-25 cm high 
Replications: 3 
Results: 9 DAT 
% of Plants with 
of the Plant 
Rate Bleaching Bleached 
Compounds 
kg ai/ha or Chlorosis or Chlorotic 
______________________________________ 
51A 1.0 100 Chl 5 Chl 
51A + 2,4-D 
1.0 + 2.6 33 Chl 2 Chl 
8D 0.5 30 Chl 20 Chl 
8D + 2,4-D 
0.5 + 2.16 
0 0 Chl* 
24D 0.25 100 Bl 18 Chl 
24D + 2,4-D 
0.25 + 2.16 
0 0 
24D 0.5 87 Bl 20 Bl 
24D + 2,4-D 
0.5 + 2.16 
0 5 Chl* 
______________________________________ 
Chl = Chlorosis 
Bl = Bleaching 
*Only slight chlorosis was seen. 
Results of greenhouse test conditions for 2,4-D (amine) antidote activity 
on surgarcane varieties CP-5122, RB-735275 and RB-725147 are as follows: 
Varieties CP-5122, RB-735275 and RB-725147 
Volume of Water: 400 liters/ha 
Method and Stage of Application: POES, sugarcane varieties at 30 cm high 
Evaluation: Bleaching at l, 2 and 3 weeks after application 
Symptoms observed and recorded are bleaching of the young sugarcone plants 
in the test, results indicate that the 2,4-D (dimethylamine) is 
independent of the rate tested and gave total protection to sugarcane from 
POES application of Compounds 24D and 8D. 
Date Rated: 1, 2 and 3 weeks after application. 
__________________________________________________________________________ 
Sugarcane Varieties 
CP-5122 RB-73525 RB-725147 
Treatments 
kg ai/ha 
1 2 3 1 2 3 1 2 3 
__________________________________________________________________________ 
24D 0.25 15 05 00 15 40 20 15 40 20 
0.50 20 60 50 20 80 70 20 80 40 
1.00 25 80 75 25 80 85 25 90 80 
24D + 2,4D 
0.25 + 1.5 
0 0 0 0 0 0 0 0 0 
0.25 + 2.0 
0 0 0 0 0 0 0 0 0 
0.25 + 2.5 
0 0 0 0 0 0 0 0 0 
0.50 + 1.5 
0 0 0 0 0 0 0 0 0 
0.50 + 2.0 
0 0 0 0 0 0 0 0 0 
0.50 + 2.5 
0 0 0 0 0 0 0 0 0 
1.00 + 1.5 
0 0 0 0 0 0 0 0 0 
1.00 + 2.0 
0 0 0 0 0 0 0 0 0 
1.00 + 2.5 
0 0 0 0 0 0 0 0 0 
4D 1.00 25 80 75 25 90 90 15 80 85 
4D + 2,4-D 
1.00 + 1.5 
20 80 80 20 60 90 10 20 60 
1.00 + 2.0 
20 70 70 20 15 30 10 0 30 
1.00 + 2.5 
10 40 70 10 15 40 10 0 20 
51A 1.00 0 0 0 0 0 0 0 0 0 
51A + 2,4-D 
1.00 + 1.5 
0 0 0 0 0 0 0 0 0 
1.00 + 2.0 
0 0 0 0 0 0 0 0 0 
1.00 + 2.5 
0 0 0 0 0 0 0 0 0 
8D 0.75 25 40 0 25 40 15 15 40 20 
8D + 2,4-D 
0.75 + 1.5 
0 0 0 0 0 0 0 0 0 
0.75 + 2.0 
0 0 0 0 0 0 0 0 0 
0.75 + 2.5 
0 0 0 0 0 0 0 0 0 
2,4-D 1.5 10 0 0 10 0 0 10 0 0 
2.0 0 0 0 0 0 0 10 0 0 
2.5 0 0 0 0 0 0 10 0 0 
__________________________________________________________________________ 
TEST FOR CONTINUED ANNUAL WEED ACTIVITY 
Annual Weed Activity: Weeds in the 2-3 leaf stage were sprayed POES 
tank-mixed. Percent activity was taken 30 days after treatment. 
______________________________________ 
% of 
Compounds 
kg ai/ha Control (XG) 
30 DAT (X BL) 
______________________________________ 
51A 1.0 91 74 
51A + 2,4-D 
1.0 + 2.6 91 86 
8D 0.5 100 75 
8D + 2,4-D 
0.5 + 2.16 100 95 
24D 0.25 100 99 
24D + 2,4-D 
0.25 + 2.16 
100 95 
24D 0.5 100 95 
24D + 2,4-D 
0.5 + 2.16 100 94 
4D 1.0 98 69 
4D + 2,4-D 
1.0 + 2.16 98 72 
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(XG) = Average of grasses: Digitaria horizontalis and Eleusine indica 
(XBL) = Average of broadleaves: Amaranthus hybridus, Acanthospermum 
hispidum, Ipomoea spp. and Portulaca oleracea 
Results show continued weed control on various grasses and broadleaf weed 
species with a sugarcane antidotally effective amount of 2,4-D with the 
herbicides. 
PERENNIAL WEED ACTIVITY 
Activity on Purple Nutsedge (Cyperus rotundus) 
New field tests on 24D/2,4-D were carried out to confirm the POES activity 
of 24D mixture plus the antidote 2,4-D on Cyperus rotundus. 
An advanced purple nutsedge stage of growth was selected for this test: 
Cyperus rotundus, 10 cm high. 
Results showed that 2,4-D helped 24D to control purple nutsedge. 24D at 
0.75+2,4-D or 24D alone at 1.0 kg ai/ha gave excellent POES control of 
purple nutsedge. 
______________________________________ 
% Degree 
of Purple 
% of Visual control 
Nutsedge Plant 
Treatments 
kg ai/ha 27 DAT 41 DAT 41 DAT 
______________________________________ 
check 0.5 573* 214* 214* 
24D 0.5 45 60 57 
24D + 2,4-D 
0.5 + 2.0 85 96 89 
24D + 2,4-D 
0.5 + 2.5 92 98 96 
24D 0.75 50 68 69 
24D + 2,4-D 
0.75 + 2.0 
83 96 93 
24D + 2,4-D 
0.75 + 2.5 
87 96 96 
24D 1.0 73 92 96 
24D + 2,4-D 
1.0 + 2.0 90 97 91 
24D + 2,4-D 
1.0 + 2.5 93 99 96 
______________________________________ 
*Number of purple nutsedge plants/m.sup.2. 
Tests carried out later under greenhouse conditions confirmed that 2,4-D 
did not change the weed activity of 24D. 
Formulations 
A formulation is the incorporation of a formulant in a form which is 
directly usable on crops and weeds. As defined herein, a "formulant" is 
the material which is to be formulated. The formulant may be either an 
antidote compound alone or an herbicide and antidote composition. The 
purpose of the formulation is to apply the formulant to the locus of a 
crop where it is desired to establish herbicidal selectivity by a 
convenient method. The "locus" may include soil, seeds, crop, crop seeds, 
seedlings and vegetation. 
The antidotes described herein can be formulated in a number of ways for 
suitable application: (a) the antidote can be formulated for application 
directly to the crop seed; (b) the antidote and herbicide may be 
formulated separately and applied separately or applied simultaneously in 
an appropriate weight ratio, e.g., as a tank mix, or (c) the antidote and 
herbicide may be formulated together in the proper weight ratio. 
Useful formulations of the compounds of this invention can be prepared in 
conventional ways. They include dusts, granules, microcapsules, pellets, 
solutions, suspensions, emulsions, wettable powders, emulsifiable 
concentrates and the like. Many of these may be applied directly to the 
locus. Sprayable formulations can be extended in suitable media and used 
at spray volumes of from a few liters to several hundred liters per 
hectare. High strength compositions are primarily used as intermediates 
for further formulation. The formulations, broadly, contain about 0.1% to 
99% by weight of active herbicide and antidote ingredient(s) and at least 
one of (a) about 0.1% to 20% surfactant(s) and (b) about 1% to 99.9% solid 
or liquid inert diluent(s). More specifically, they can contain these 
ingredients in the following approximate proportions. 
TABLE 2 
______________________________________ 
Active 
Herb. & Ant. 
Weight Percent* 
Ingredients 
Diluent(s) 
Surfactant(s) 
______________________________________ 
Wettable Powders 
20-90 0-74 1-10 
Oil Suspensions 
3-50 40-95 0-15 
Emulsions, Solutions, 
(including Emulsifiable 
Concentrates) 
Aqueous Suspension 
10-50 40-84 1-20 
Dusts 1-25 70-99 0-5 
Granules and Pellets 
0.1-95 5-99.9 0-15 
High Strength 90-99 0-10 0-2 
Compositions 
______________________________________ 
*Active ingredient plus at least one of a Surfactant or a Diluent equals 
100 weight percent. 
Lower or higher levels of active ingredient can, of course, be present 
depending on the intended use and the physical properties of the compound. 
Higher ratios of surfactant to active ingredient are sometimes desirable, 
and are achieved by incorporation into the formulation or by tank mixing. 
Dusts are free-flowing powder compositions containing the formulant 
impregnated on a particulate carrier. The particle size of the carriers is 
usually in the approximate range of 30 to 50 microns. Examples of suitable 
carriers are talc, bentonite, diatomaceous earth, and pyrophyllite. The 
composition generally contains up to 50% of formulant. Anti-caking and 
anti-static agents may also be added. Dusts may be applied by spraying 
from boom sprayers, hand sprayers or airplanes. 
Wettable powders are finely divided compositions comprising a particular 
carrier impregnated with the formulant and additionally containing one or 
more surface active agents. The surface active agent promotes rapid 
dispersion of the powder in an aqueous medium to form stable, sprayable 
suspensions. A wide variety of surface active agents can be used, for 
example, long chain fatty alcohols and alkali metal salts of the sulfated 
fatty alcohols; salts of sulfonic acid; esters of long chain fatty acids; 
and polyhydric alcohols, in which the alcohol groups are free, 
omega-substituted polyethylene glycols of relatively long chain length. A 
list of surface active agents suitable for use in agriculture formulations 
can be found in Wade Van Valkenburg, Pesticide Formulations (Marcel 
Dekker, Inc., N.Y., 1973) at pages 79-84. 
Granules comprise the formulant impregnated on a particulate inert carrier 
having a particle size of about 1 to 2 millimeters (mm) in diameter. The 
granules can be made by spraying a solution of the formulant in a volatile 
solvent onto the granular carrier. Examples of suitable carries for the 
preparation of granules include clay, verminculite sawdust, and granular 
carbon. 
Microcapsules and other slow release formulations are advantageous as 
formulations to deliver and distribute the active ingredients. 
Microcapsules consist of fully enclosed droplets or granules containing 
the active materials in which the enclosing material is an inert porous 
membrane, arranged to allow escape of the enclosed materials to the 
surrounding medium at controlled rates over a specified period of time. 
Encapsulated droplets are typically about 1 to 50 microns in diameter. The 
enclosed liquid typically constitutes about 50 to 95% of the weight of the 
entire capsule, and may contain an amount of solvent in addition to the 
active materials. Encapsulated granules are characterized by porous 
membranes sealing the openings of the granule carrier pores, trapping the 
liquid containing the active components inside for controlled release. A 
typical granule size ranges from 1 millimeter to 1 centimeter in diameter. 
In agricultural usage, the granule size is generally about 1 to 2 
millimeters in diameter. Granules formed by extrusion, agglomeration or 
prilling are useful in the present invention as well as materials in their 
naturally occurring form. Examples of such carriers are vermiculite, 
sintered clay granules, kaolin, attapulgite clay, sawdust and granular 
carbon. Useful encapsulating materials include natural and synthetic 
rubbers, cellulosic materials, styrene-butadiene copolymers, 
polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, 
polyurethanes and starch xanthates. 
Emulsifiable concentrates consist of an oil solution of the formulant plus 
an emulsifying agent. Prior to use, the concentrate is diluted with water 
to form a suspanded emulsion of oil droplets. The emulsifiers used are 
usually a mixture of anionic and nonionic surfactants. Other additives, 
such as suspending agents and thickeners, may be included in the 
emulsifiable concentrate. 
When the formulant is an antidote and herbicide composition, the proportion 
of antidote compound to herbicide compound generally ranges from 
approximately 0.001 to 30 parts by weight of the antidote compound per 
weight of the herbicide compound. 
Formulations generally contain several additives in addition to the 
formulant and carrier or agent. Among these are inert ingredients, diluent 
carriers, organic solvents, water, oil and water, water in oil emulsions, 
carriers of dusts and granules, and surface active wetting, dispersing and 
emulsifying agents. Fertilizers, e.g., ammonium nitrate urea and 
superphosphate, may be included. Aids to rooting and growth, e.g., 
compost, manure, humus and sand, may also be included. 
Alternatively, the antidote compounds and herbicide and antidote 
compositions of this invention can be applied to a crop by addition of the 
formulant to irrigation water supplied to the field to be treated. This 
method of application permits the penetration of the compositions into the 
soil as the water is absorbed. 
As another alternative, the formulant can be applied to the soil in the 
form of a solution in a suitable solvent. Solvents frequently used in 
these formulations include kerosene, fuel oil, xylene, petroleum fractions 
with boiling ranges above xylene and aromatic petroleum fractions rich in 
methylated naphthalenes. Liquid solutions, like dusts, may be applied by 
spraying from boom and hand sprayers or airplanes. 
EXAMPLE 
Dusts: The following substances are used to formulate (a) 5% and (b) a 2% 
dust: 
______________________________________ 
(a) - 5 parts of active substance 
95 parts of talc; 
(b) 
2 parts of active substance 
1 part of highly dispersed silicic acid 
97 parts of talc. 
______________________________________ 
The active substances are mixed with the carriers and ground and in this 
form can be processed to dusts for application. 
EXAMPLE 
Granulate: The following substances are used to formulate a 5% granulate: 
______________________________________ 
5 parts of active substance 
0.25 part of epichlorohydrin 
0.25 part of cetyl polyglycol ether 
3.25 parts of polyethylene glycol 
91 parts of kaolin (particle size 0.3-0.8 mm). 
______________________________________ 
The active substance is mixed with epichlorohydrin and the mixture is 
dissolved in 6 parts of acetone. Then polyethylene glycol and cetyl 
polyglycol ether are added. The resultant solution is sprayed on kaolin 
and the acetone is evaporated in vacuo. 
EXAMPLE 
Wettable powders: The following constituents are used to formula (a) a 70%, 
(b) a 40%, (c) and (d) a 25% and (e) a 10% wettable powder. 
______________________________________ 
(a) 
70 parts of active substance 
5 parts of sodium dibutylnaphthylsulfonate 
3 parts of naphthalenesulfonic acid/phenolsulfonic 
acid/formaldehyde condensate (3:2:1) 
10 parts of kaolin 
12 parts of Champagne chalk 
(b) 
40 parts of active substance 
5 parts of sodium ligninsulfonate 
1 part of sodium dibutylnaphthalenesulfonic acid 
54 parts of silicic acid 
(c) 
25 parts of active substance 
4.5 parts of calcium ligninsulfate 
1.9 parts of Champagne chalk/hydroxyethyl cellulose 
mixture (1:1) 
1.5 parts of sodium dibutylnaphthalenesulfonate 
19.5 parts of silicic acid 
19.5 parts of Champagne chalk 
28.1 parts of kaolin 
(d) 
25 parts of active substance 
2.5 parts of isooctylphenoxy-polyethylene-ethanol 
1.7 parts of a Champagne chalk/hydroxyethyl cellulose 
mixture (1:1) 
8.3 parts of sodium aluminum silicate 
16.5 parts of kieselguhr 
46 parts of kaolin 
(e) 
10 parts of active substance 
3 parts of a mixture of the sodium salts of saturated fatty 
alcohol sulfates 
5 parts of naphthalenesulfonic acid/formaldehyde condensate 
82 parts of kaolin. 
______________________________________ 
The active substances are intimately mixed in suitable mixers with the 
additives and ground in appropriate mills and rollers. Wettable powders of 
excellent wettability and suspension power are obtained. These wettable 
powders can be diluted with water to give suspensions of the desired 
concentration and can be used in particular for treating parts of plants. 
EXAMPLE 
Emulsifiable concentrate: The following substances are used to formulate a 
25% emulsifiable concentrate: 
______________________________________ 
25 parts of active substance 
2.5 parts of epoxidized vegetable oil 
10 parts of an alkylarylsulfonate/fatty alcohol polyglycol 
ether mixture 
5 parts of diethylformamide 
57.5 parts of xylene. 
______________________________________ 
By diluting such a concentrate with water it is possible to prepare 
emulsions of the desired concentrations, which are especially suitable for 
leaf application.