Disclosed herein are 2- or 6-fluoromethyl-3-pyridinecarboxylate derivatives with 3- or 5-dialkylamino substitution which are useful as herbicides.

This invention relates to a new class of 2,6-substituted 
pyridinedicarboxylic acid derivatives having activity as herbicides, to 
their use as herbicides, and to herbicidal compositions containing them. 
Pyridine derivatives have, for many years, been investigated for use in 
the biological sciences. Pyridine dicarboxylate compounds useful as 
herbicides are described in U.S. Pat. No. 4,692,184. These compounds have 
fluorinated methyl groups at the 2- and 6-positions and carboxylic acids 
or their derivatives at the 3- and 5-positions and are characterized 
further by a 4-position substituent in which the atom attached to the 
pyridine ring is a carbon atom, such as alkyl, alkoxyalkyl, 
alkylthioalkyl, aralkyl, and like moieties. 
Other pyridine compounds include those which contain fluorinated methyl 
groups at the 2- and 6-positions, carboxylic acids or their derivatives at 
the 3- and/or 5-positions and at the 4-position have a substituent group 
beginning with a hetero atom selected from O, S, N and P. These compounds 
are likewise useful as herbicides. 
Other herbicidal pyridines are those of U.S. Pat. No. 4,609,399 which have 
a fluorinated methyl group at the 2-position, a carboxylic acid group or 
derivative thereof at the 3- and/or 5-position, and alkoxy groups at the 
4- and 6-positions. 
More relevant to the compounds of this invention are those disclosed in 
U.S. Pat. No. 4,885,026; which are 5-amino pyridine 3-carboxylate 
derivatives in which the 5-amino group is a secondary amine; i.e., one 
hydrogen remains on the nitrogen. 
BRIEF DESCRIPTION OF THE INVENTION 
It is an object of this invention to provide novel pyridine compounds, as 
well as herbicidal methods and compositions utilizing such compounds, 
which have surprisingly superior herbicidal activity compared to the 
corresponding 5-monoalkylamino pyridine compounds of the prior art. 
The novel compounds of this invention are useful as herbicides or 
intermediates which can be converted to herbicides and are represented by 
the generic formula 
##STR1## 
wherein: one of A and B is selected from the group consisting of 
fluorinated methyl and chlorofluorinated methyl radicals, and the other is 
selected from the group consisting of fluorinated methyl, 
chlorofluorinated methyl and lower alkyl radicals; 
E is selected from the group consisting of alkyl, alkenyl, cycloalkyl, 
cycloalkylalkyl, haloalkyl, and alkylthioalkyl radicals; 
G is selected from the group consisting of carboxylic acid moieties and 
their alkyl ester, alkyl thioester, and alkenyl ester derivatives; and 
D is --NRR' in which R and R' are the same or different lower alkyl groups, 
each optionally substituted with one or more groups selected from halo, 
amino, alkylthio, alkylsulfonyl, and alkoxy radicals. 
As used herein throughout the specification and claims, the following terms 
have the following meanings: 
The term "alkyl" means herein both straight and branched chain saturated 
hydrocarbon radicals having 1 to 7 carbon atoms, unless a different carbon 
number range is expressly stated. Examples of such radicals include, but 
are not limited to, ethyl, methyl, n-propyl, 1-ethylpropyl, 
1-methylpropyl, n-butyl, 1,1-dimethylethyl, 2,2-dimethylpropyl, pentyl, 
isobutyl, isopropyl, and the like. 
The term "cycloalkyl" means saturated cyclic radicals having 3 to 7 carbon 
atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and 
cycloheptyl. 
The terms "alkenyl" and "alkynyl" herein mean alkenyl and alkynyl groups 
having 2 to 7 carbon atoms. Examples of such alkenyl groups include 
ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 
2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-methylethenyl, and the like. 
Examples of such lower alkynyl groups include ethynyl, 1-propynyl, 
2-propynyl, and so forth. 
The term "cycloalkylalkyl" is intended to mean alkyl radicals having 1 to 3 
carbon atoms which is substituted with a cycloalkyl group having 3 to 7 
carbon atoms. 
The term "haloalkyl" is intended to mean an alkyl radical (as defined 
above) substituted with one or more halogen atoms selected from F, Cl, Br, 
and I, "haloalkenyl" and "haloalkynyl" refer to alkenyl and alkynyl 
radicals substituted with one or more halogens. 
The term "alkanoyl" as used herein means a radical derived from an alkanoic 
acid, and includes formyl, acetyl (or methylcarbonyl), propanoyl (or 
ethylcarbonyl), cyclopropylformyl (or cyclopropylcarbonyl), and the like. 
The term "cation" means any monovalent cation derived from a base which is 
capable of forming a salt. Typical cations include, but are not limited 
to, alkali metals such as sodium, potassium, and lithium; alkaline earth 
metals such as calcium and magnesium; and ammonium salts, organic amines, 
sulfonium and phosphonium salts, and other salt complexes. 
The term "fluorinated methyl" means herein methyl radicals having one or 
more fluorine atoms attached thereto, and includes radicals wherein all 
hydrogen atoms replaced by fluorine. 
The term "chlorofluorinated methyl" means herein a methyl radical having at 
least one hydrogen replaced by fluorine and at least one other hydrogen 
replaced by chlorine. 
The term "halogen" and its combining form "halo" are used herein to refer 
to fluorine, chlorine, bromine, and iodine.

DETAILED DESCRIPTION OF THE INVENTION 
As used throughout the specification, including the Examples, the following 
abbreviations have the following meanings: 
LDA--lithium diisopropylamide 
THF--tetrahydrofuran 
DME--dimethoxyethane 
DBU--1,8-diazabicyclo-[5.4.0]-undec-7-ene 
DMF--N,N-dimethylformamide 
ETFAA--ethyl trifluoroacetoacetate 
MCPBA--m-chloroperbenzoic acid 
HPLC--high pressure liquid chromatography 
TLC--thin layer chromatography 
n-BuLi--n-butyl lithium 
DMSO--dimethyl sulfoxide 
Pd/C--hydrogenation catalyst which is palladium deposited on finely-divided 
carbon 
TsCl--tosyl chloride. 
Dialkylamino pyridine compounds of this invention are prepared by reduction 
of an alkanoyl alkylamino pyridine compound, which is in turn prepared 
either by reaction of a monoalkylamino pyridine with an acid chloride or 
by reaction of an alkanoylamino pyridine with a substituted or 
unsubstituted alkyl halide. The monoalkylamino pyridine, if used in the 
preparation, is made by reduction of an alkanoylamino pyridine, which is 
prepared by reaction of a 3- or 5-amino pyridine and an acid chloride. The 
3- or 5-amino pyridine is prepared from a 3- or 5-chlorocarbonyl pyridine. 
Aminopyridines and their preparation from the chlorocarbonyl pyridines (or 
pyridine acid chlorides) are described in more detail in U.S. Pat. No. 
4,885,026 which corresponds to European Patent Publication No. 0252055, 
the disclosure of which is incorporated herein by reference. 
Preparation of the chlorocarbonyl pyridines (pyridine acid chlorides) is 
illustrated below in Steps 1-9. Preparation of primary amino pyridines is 
shown below in Examples F-1 to F-3. Preparation of the alkanoyl amine 
precursors is shown in Examples G-1 to G-5, while Examples H-1 and H-2 
illustrate preparation of monoalkylamine precursors of the compounds of 
this invention. Preparation of the pyridine 5-dialkylamine compounds of 
this invention is shown following these examples in Examples 1 to 12. 
PREATION OF PYRIDINE 5-ACID CHLORIDE STARTING MATERIALS 
The compounds of this invention are prepared using as a starting material a 
pyridine 3,5-dicarboxylic acid mono-ester mono-chloride or dichloride. 
Steps 1-9 which follow set out in detail the preparation of three specific 
acid halides which are used as starting materials for the compounds of 
this invention. Other acid halides may be readily prepared using the 
procedures of Steps 1-9 by varying the ketoester and aldehyde used in Step 
1 to obtain the desired substituents in the pyridinedicarboxylate product. 
Other suitable pyridinecarboxylate acid halide starting materials are 
shown in U.S. Pat. No. 4,692,184 in Examples 44-51 and 82-83 inclusive, 
the disclosure of which is incorporated herein by reference in its 
entirety. Other acid halide starting materials may be readily prepared 
using the techniques set out in that U.S. Patent. 
The following Steps 1-9 illustrate an example of the procedures for 
preparation of the acid halide compounds which are the starting materials 
for making the amines of the present invention. In these steps, a 
.beta.-ketoester is reacted with an aldehyde to form a pyran (Step 1). The 
pyran is then reacted with ammonia to form a dihydroxypiperidine (Step 2), 
which is dehydrated to make a dihydropyridine compound (Step 3). The 
dihydropyridine is then oxidized or dehydrofluorinated to prepare a 
pyridinedicarboxylate compound (Step 4). 
The ester groups of the pyridinedicarboxylate compound are the ester groups 
of the .beta.-ketoester, and the 4-position of the pyridine is substituted 
with the same substituent as is on the aldehyde reagent. 
When the pyridinedicarboxylate is substituted at the 2- or 6-position with 
a trifluoromethyl radical and at the other of these positions with a 
difluoromethyl radical, hydrolysis of the pyridine dicarboxylate compound 
occurs selectively on the side having the CF.sub.2 H group when one 
equivalent of a base such as KOH is employed in the hydrolysis (Step 8). 
When two equivalents of base or more are employed, the dicarboxylate is 
hydrolyzed to the diacid (Step 5). The diacid may be converted to the 
diacid chloride by treatment with a chlorinating agent such as SOCl.sub.2 
or PCl.sub.5. Following this conversion, treatment with one equivalent of 
an alcohol selectively esterifies the diacid chloride on the chloride 
group adjacent to the CF.sub.2 H group. 
STEP 1 
Preparation of dimethyl 
2,6-bis(trifluoromethyl)-2,6-dihydroxy-4-isobutyl-tetrahydro-3,5-pyrandica 
rboxylate 
To a mechanically stirred mixture of 280 g (2.0 mole) of 80% pure methyl 
trifluoroacetoacetate and 86 g (1.0 mole) of isovaleraldehyde is added 1 
ml of piperidine. An exothermic reaction occurs and the temperature of the 
reaction mixture reaches 105.degree. C. After 5 hours of stirring, the 
reaction mixture is triturated with 450 ml of hexane and 30 ml of ether 
and cooled with a dry ice bath to give 1.68 g of a first crop, m.p. 
83.degree.-87.degree. C. and 14.51 g of a second crop, m.p. 
67.degree.-73.degree. C. 
The first crop is the desired product which contains a mixture of 5:1 cis 
and trans isomers. 
The second crop is a 2:1 mixture of cis and trans isomers. The mother 
liquor is concentrated to give 344 g of a residue which is a crude mixture 
of cis and trans isomer of the desired product. 
STEP 2 
Preparation of dimethyl 
2,6-bis(trifluoromethyl)-2,6-dihydroxy-4-isobutyl-3,5-piperidinedicarboxyl 
ate 
To a solution of 344 g (0.920 mole) crude product from Step 1 in 500 ml of 
tetrahydrofuran (THF) is passed 58 g (3.41 mole) of gaseous ammonia for 3 
hours. The reaction mixture is concentrated and the residue (332 g) is 
recrystallized from hexane-ether to give 53.7 g (13% yield from methyl 
trifluoroacetoacetate) of the desired product as a white solid, m.p. 
102.degree.-106.degree. C. 
The mother liquor is concentrated to provide more of the crude desired 
product. 
STEP 3 
Preparation of a 2:1 mixture of dimethyl 
2,6-bis(trifluoromethyl)-1,4-dihydro-4-isobutyl-3,5-pyridinedicarboxylate 
and its 3,4-dihydropyridine isomer 
To an ice water cooled mixture of 200 ml of concentrated sulfuric acid and 
200 ml of methylene chloride is added 48.7 g (0.115 mole) of the product 
of Step 2 at once. The reaction mixture is stirred for 20 minutes and 
poured into 1 L of ice water. The methylene chloride layer is separated 
and washed once with 100 ml of saturated sodium bicarbonate, dried and 
concentrated to give 28.0 g (64.6%) of crude product. A portion (5.0 g) of 
this product is kugelrohr distilled at 0.5 torr (pot temperature at 
120.degree. C.) to give 4.8 g of the desired product, n.sub.D.sup.25 
1.4391. 
Step 3 product may be prepared in better overall yield without isolation of 
Step 1 and Step 2 product by the following procedure: 
To a mechanically stirred mixture of 340.3 g (1.98 mol) of 98.9% pure 
methyl trifluoroacetoacetate (MTFAA), 100 mL of toluene and 0.86 g (0.01 
mol) of piperidine was added 90.5 g (1.03 mol) of isovaleraldehyde in 20 
minutes. The reaction mixture exothermed causing a rise of temperature to 
83.degree. C. The reaction mixture was maintained at 80.degree. C. for 3 
hours. .sup.19 F NMR showed that the reaction was 89% complete. Heat was 
removed, and the reaction mixture was diluted with 125 mL of toluene and 
stirred overnight (16 hours). Gaseous ammonia was passed through the 
reaction mixture, the exotherm caused a rise of temperature to 68.degree. 
C. in 50 minutes. A water cooling bath was applied to the reaction vessel 
to reduce the reaction temperature to 53.degree. C. while ammonia was 
passed continuously. A total of 47.3 g (2.78 mol) of ammonia was passed in 
1.5 hours. The reaction mixture was diluted with 100 mL of toluene. A 
Claisen distillation head was attached to the reaction vessel. 
Excess ammonia and parts of toluene were removed in vacuo (water aspirator) 
while temperature was maintained at 26.degree. C. An additional 200 mL of 
toluene was added, and the distillation was continued to remove a total of 
200 mL of distillate in 1.5 hours. The reaction mixture was diluted with 
100 mL of toluene and cooled to 5.degree. C. with an ice bath. Sulfuric 
acid (453 g, 4.53 mol) was added in 5 minutes. The exotherm caused the 
temperature to rise to 25.degree. C. The temperature gradually subsided to 
5.degree. C. in 10 minutes and was maintained at 5.degree. C. for 40 
minutes. An additional 95 g (0.95 mol) of sulfuric acid was added, and the 
reaction mixture was stirred at 5.degree. C. for 20 minutes before being 
poured into a mixture of 500 mL of toluene and 2 L of ice water. The 
toluene layer was separated and the aqueous layer was extracted once with 
500 mL of toluene. The combined toluene extracts were washed successively 
with 500 mL of water, 500 mL of saturated aqueous NaHCO.sub.3, 500 mL of 
brine and concentrated in vacuo to afford 363.6 g of an oil. GC area 
percent analysis indicated that the oil contained 9% of 
3,4-dihydropyridine isomer and 75.4% of 1,4-dihydropyridine isomer 
corresponding to an overall yield of 82.9% from MTFAA. 
STEP 4 
Preparation of dimethyl 
2-(difluoromethyl)-6-(trifluoromethyl)-4-isobutyl-3,5-pyridinedicarboxylat 
e 
(a) Reaction of the Product of Step 3 with DBU 
A mixture of 23.0 g (0.0591 mole) of the product of Step 3, 12.2 g (0.077 
mole) of 96% pure DBU, and 100 ml of THF is held at reflux for 3 days and 
poured into 250 ml of 3N HCl. The oil precipitate is extracted into ether 
(2.times.100 ml). The ether extracts are dried (MgSO.sub.4) and 
concentrated to give 14.4 g of an oil which, according to .sup.1 H NMR, 
contained the desired product and acidic products. This oil is dissolved 
in ether and extracted with 100 ml of saturated sodium bicarbonate. The 
ether layer is dried (MgSO.sub.4) and concentrated to give 8.9 g of an oil 
which is 71% pure desired product (by .sup.19 F NMR). 
The sodium bicarbonate extract is acidified with concentrated HCl to give 
an oil which is extracted into ether. The ether layer is dried 
(MgSO.sub.4) and concentrated to give 4.8 g of a residue which contained 
monocarboxylic acid and dicarboxylic acid (9:1) derived from the desired 
product. This residue is treated with 3.0 g (0.0217 mole) of potassium 
carbonate, 20 ml of methyl iodide, and 50 ml of acetone. The mixture is 
held at reflux for 42 hours and concentrated. The residue is treated with 
water and extracted with ether (2.times.100 ml). The ether layer is dried 
and concentrated. The residue is kugelrohr distilled at 1 torr (pot 
temperature of 130.degree. C.) to give 5.1 g (23.4% from Step 3) of the 
desired product as an oil, n.sub.D.sup.25 1.4478. This product 
crystallizes after standing, m.p. 36.degree.-37.degree. C. 
The 71% pure desired product described previously was purified by HPLC 
using 3% ethyl acetate/cyclohexane as eluent to give an earlier fraction 
(0.79 g, retention time 7-8.5 minutes) which was identified as methyl 
6-(difluoromethyl)-4-(isobutyl)-2-(trifluoromethyl)-3-pyridinecarboxylate. 
The second fraction (retention time 8.5-18.5 minutes) is an additional 6.4 
g (29.4%) of pure desired product, n.sub.D.sup.25 1.4474. 
(b) Reaction of the Product of Step 3 with Tributylamine 
A mixture of 38.9 g of an 80% pure product of Step 3 and 20.5 g of 
tributylamine is heated to 155.degree. C. in 30 minutes. The reaction 
mixture was cooled to 30.degree. C. and diluted with 100 ml of toluene. 
The toluene solution is washed successively with 6N hydrochloric acid, 
saturated sodium bicarbonate, and brine, dried and concentrated to give 
36.4 g of a 73% pure product which corresponds to an 86% yield. This 
reaction can also be carried out in excess of tributylamine (10 
equivalents) giving essentially similar results. 
(c) Reaction of the Product of Step 3 with Tributylamine in Toluene 
A mixture of 38.9 g of an 80% pure product of Step 3, 20.4 g of 
tributylamine and 30 ml of toluene is heated to 115.degree. C. in 40 
minutes and held at 115.degree. C. for 1 hour and 40 minutes. The reaction 
mixture is cooled and worked up as in (b) above to give 36.3 g of a 76% 
pure product which corresponds to a 90% yield. 
(d) Reaction of the Product of Step 3 with Tributylamine 
A mixture of 11.8 g of an 80% pure product of Step 3 and 3.34 g of 
triethylamine is heated at 100.degree. C. for 10 minutes, then at 
125.degree. C. for 10 minutes. The reaction mixture was cooled and worked 
up as in (b) above to give 8.14 g of a 76% pure product which corresponds 
to a 63% yield. 
(e) Reaction of the Product of Step 3 with 2,6-Lutidine in the Presence of 
a Catalytic Amount of DBU 
A mixture of 5.0 g of product of Step 3 and 2.13 g of 2,6-lutidine is 
heated at 143.degree. C. for 30 minutes. Two drops of DBU are added and 
the reaction mixture is heated for additional 1 hour and 30 minutes, 
cooled and worked up as in (b) above to give 4.23 g of the desired 
product. The reaction can also be carried out in excess of 2,6-lutidine 
and catalytic amount of DBU without solvent or in the presence of toluene 
as solvent giving similar results. 
STEP 5 
Preparation of 
2-(difluoromethyl)-6-(trifluoromethyl)-4-isobutyl-3,5-pyridinedicarboxylic 
acid 
A 5-liter flask was charged with 894 g (2.42 mol) of the compound of Step 4 
and 1 liter of water. To this was added a solution of 574 g (8.7 mol) of 
KOH in 800 ml of water. The mixture was refluxed overnight, after which 
HPLC showed that the reaction was complete. The flask was cooled to room 
temperature, acidified with HCl, and stirred until the organic phase 
solidified. The solids were filtered, washed with water, and dried in a 
fluid bed dryer. The diacid was obtained (756 g, 91.6% yield) as a brown 
solid. 
STEP 6 
Preparation of 
3,5-bis-(chlorocarbonyl)-2-(difluoromethyl)-4-isobutyl-6-(trifluoromethyl) 
pyridine 
The diacid product of Step 5 (37.06 g, 0.108 mole) was refluxed with 150 ml 
SOCl.sub.2 for three hours. At this time, .sup.19 F NMR indicated the 
reaction was complete. The excess SOCl.sub.2 was removed by rotary 
evaporation, leaving a dark oil which was the bis-acid chloride. This was 
Kugelrohr distilled at 100.degree. C. to give a colorless oil. 
STEP 7 
Preparation of methyl 
5-(chlorocarbonyl)-2-(difluoromethyl)-4-isobutyl-6-(trifluoromethyl)pyridi 
ne-3-carboxylate 
The product of Step 6 was then dissolved in 100 ml THF followed by 100 ml 
methanol. After 21/2 hours the solvent was evaporated, leaving 31.2 g 
white solid, m.p. 71.degree.-75.degree. C. in 77% yield. 
STEP 8 
Preparation of 
2-(difluoromethyl)-4-isobutyl-6-(trifluoromethyl)-3,5-pyridinedicarboxylic 
acid, 5-methyl ester 
A 1-liter 4-necked flask was charged with 300 g of product of Step 4 and 
about 200 ml ethanol. In a separate flask was combined 59.14 g (0.896 mol) 
of 85% KOH and about 100 ml of water. The aqueous solution was poured into 
the organics and the flask was equipped with a mechanical stirrer, 
thermometer, nitrogen inlet and a water cooled consenser. The reaction 
mixture was heated to reflux, refluxed for 45 minutes and was cooled. The 
reaction mixture was concentrated and the concentrate was diluted with 
water and extracted once with ethyl ether. The ether extract (to remove 
starting material) was discarded. The aqueous solution was acidified with 
concentrated HCl and the orange precipitate that resulted was extracted 
with ethyl ether. The aqueous solution was extracted with ether 3 times. 
The ether extracts were combined and dried over anhydrous magnesium 
sulfate, filtered and concentrated to yield 253.13 g (87.5% yield) of the 
monoacid. 
STEP 9 
Preparation of methyl 
2-(difluoromethyl)-3-(chlorocarbonyl)-4-isobutyl-6-(trifluoromethyl)- 
5-pyridinecarboxylate 
The acid (253 g, 0.7121 mol) from Step 8 was refluxed for 24 hours in 
approximately 250-300 ml of thionyl chloride. The reaction mixture was 
concentrated to yield 244.59 g of acid chloride in 91.9% yield. 
n.sub.D.sup.25 1.4614. 
Steps 1-9 above have illustrated the preparation of pyridine carboxylic 
acid chlorides having a particular set of 2,- 6,- and 4-substituents. 
Preparation of other acid chlorides will be clear from the foregoing and 
by reference to U.S. Pat. No. 4,692,184. 
PREATION OF 5-AMINO PYRIDINES 
The next step in the sequence for preparing compounds of the present 
invention is the conversion of the carboxylic acid chloride function of 
the starting materials shown above to the correspondingly-substituted 
5-amino or 3,5-bis amino pyridine. The general procedure for this 
conversion is shown in Examples F-1 to F-3. 
EXAMPLE F-1 
3-Pyridinecarboxylic acid, 
5-amino-2-(difluoromethyl)-4-(2-methylpropyl)-6-(trifluoromethyl)-, methyl 
ester 
To a stirred solution of 24.4 g (0.375 mol) sodium azide in 100 mL water 
and 200 mL of acetone at room temperature was added a solution of 55.8 g 
(0.15 mol) product of Step 7 above in 100 mL of acetone in portions. 
Following a mild exotherm, the mixture was stirred at room temperature for 
4 h. The reaction mixture was concentrated, and diluted with 200 mL water. 
The mixture was extracted with ethyl ether (2.times.200 mL), and the 
combined extracts were washed with water (2.times.200 mL), dried 
(MgSO.sub.4), and evaporated. The crude product was then vacuum distilled 
(130.degree. C., 2 mm Hg) by Kugelrohr apparatus to afford 44.0 g (91%) of 
the desired product as a pale yellow solid; mp 48.degree.-50.degree. C. 
The following amines were made in a similar manner using the general 
procedure for Example A-1 and starting with the indicated pyridine acid 
chloride. 
EXAMPLE F-2 
3-Pyridinecarbothioic acid, 
5-amino-4-(2-methylpropyl)-6-(difluoromethyl)-2-(trifluoromethyl)-, 
S-methyl ester 
This compound is made from 3-pyridinecarbothioic acid, 
5-(chlorocarbonyl)-4-(2-methylpropyl)-6-(difluoromethyl)-2-(trifluoromethy 
l)-, S-methyl ester. This compound appears as Example 168 in U.S. Pat. No. 
4,885,026. 
EXAMPLE F-3 
3-Pyridinecarboxylic acid, 
5-amino-2-(difluoromethyl)-4-(cyclopropylmethyl)-6-(trifluoromethyl)-, 
methyl ester 
65% from 3-pyridinecarboxylic acid, 
5-(chlorocarbonyl)-4-(cyclopropylmethyl)-2-(difluoromethyl)-6-(trifluorome 
thyl)-, methyl ester; n.sub.D.sup.25 =1.5885. 
PREATION OF ALKANOYLAMINO PRECURSORS 
The alkanoyl amine precursors to compounds of this invention are made as 
shown in the following Examples G-1 to G-5. 
EXAMPLE G-1 
3-Pyridinecarboxylic acid, 
2-(difluoromethyl)-5-(formylamino)-4-(2-methylpropyl)-6-(trifluoromethyl)- 
, methyl ester 
To an ice-cold solution of formic-acetic anhydride (prepared by mixing 76 
mL of acetic anhydride and 38 mL of 80% formic acid) was added 9.72 g 
(0.03 mol) of product of Example F-1 and the mixture was stirred at room 
temperature for 48 h. The reaction mixture was then concentrated by 
distillation under vacuum (70.degree. C., 0.7 torr) and the resulting oily 
residue was triturated with hexane to obtain a white solid. 
Recrystallization of the crude material from hexane-ether afforded 9.5 g 
(89%) of product as colorless crystals: mp 119.degree.-120.degree. C. 
The compounds of Examples G-2 to G-5 below were prepared using the same 
general procedure as that shown in Example G-1. 
EXAMPLE G-2 
3-Pyridinecarboxylic acid, 
5-(acetylamino)-2-(difluoromethyl)-4-(2-methylpropyl)-6-(trifluoromethyl)- 
, methyl ester 
A solution of 6.52 g (0.02 mol) of product of Example F-1 in 30 mL of 
acetyl chloride was stirred overnight at room temperature. Evaporation of 
acetyl chloride by vacuum distillation (60.degree. C., 2 mm) and 
trituration of the resulting residue with hexane-ether afforded 6.78 g 
(92%) of product as a white solid: mp 188.degree.-189.degree. C. 
EXAMPLE G-3 
3-Pyridinecarboxylic acid, 
6-(difluoromethyl)-5-(formylamino)-4-(2-methylpropyl)-2-(trifluoromethyl)- 
, methyl ester 
This compound is prepared from product of Example F-1 and formic-acetic 
anhydride. It appears as Example 174 of U.S. Pat. No. 4,885,026. 
EXAMPLE G-4 
3-Pyridinecarbothioic acid, 
6-(difluoromethyl)-5-(formylamino)-4-(2-methylpropyl)-2-(trifluoromethyl)- 
, S-methyl ester 
82% yield from product of Example F-2 as an off-white solid: mp 
135.degree.-136.degree. (cyclohexane). 
EXAMPLE G-5 
3-Pyridinecarboxylic acid, 
4-(cyclopropylmethyl)-2-(difluoromethyl)-5-(formylamino)-6-(trifluoromethy 
l)-, methyl ester 
81.6% yield from product of Example F-3 as a white crystalline solid: mp 
119.degree.-120.degree. C. (cyclohexane). 
PREATION OF ALKYLAMINO PRECURSORS 
Preparation of the monoalkyl amine compounds is shown in the following 
Examples H-1 and H-2. 
EXAMPLE H-1 
3-Pyridinecarboxylic acid, 
2-(difluoromethyl)-5-(methylamino)-4-(2-methylpropyl)-6-(trifluoromethyl)- 
, methyl ester 
61% yield from product of Example G-1 using the procedure shown under 
Example 1 as a pale yellow liquid: n.sub.D.sup.25 =1.5855. 
EXAMPLE H-2 
3-Pyridinecarboxylic acid, 
2-(difluoromethyl)-5-(ethylamino)-4-(2-methylpropyl)-6-(trifluoromethyl)-, 
methyl ester 
Prepared similarly to the procedure shown under Example 1 in 91% yield from 
product of Example G-2 as a colorless liquid: n.sub.D.sup.25 =1.5833. 
PREATION OF ALKYLALKANOYLAMINO PRECURSORS 
EXAMPLE J-1 
3-Pyridinecarboxylic acid, 
5-[(cyclopropylcarbonyl)methylamino]-2-(difluoromethyl)-4-(2-methylpropyl) 
-6-(trifluoromethyl)-, methyl ester 
A solution of 6.8 g (0.02 mol) of product of Example H-1 and 2.5 g (0.024 
mol) of cyclopropane carboxylic acid chlorine in 50 mL of toluene was 
heated at reflux for 48 h. Evaporation of the solvent under reduced 
pressure gave an oil which solidified upon trituration with petroleum 
ether. Recrystallization of the crude product from hexane afforded 5.23 g 
(64%) of product as a white solid: mp 74.degree.-76.degree. C. 
EXAMPLE J-2 
3-Pyridinecarboxylic acid, 
2-(difluoromethyl)-5-(ethylformylamino)-4-(2-methylpropyl)-6-(trifluoromet 
hyl)-, methyl ester 
To a solution of 6.37 g (0.018 mol) of product of Example G-1 in 25 mL of 
dry THF at -78.degree. was added 18 mL (0.018 mol) of 1M sodium 
bis(trimethylsilyl)amide in THF. After 1 h, 19.5 g (0.125 mol) of ethyl 
iodide was added and the mixture was slowly warmed to room temperature. 
The solution was then heated at reflux for 10 h. after cooling to room 
temperature, 25 mL of saturated ammonium chloride solution was added and 
the mixture was extracted with ethyl acetate (3.times.100 mL). The 
combined organic layers were washed with water, dried (MgSO.sub.4), and 
evaporated. Chromatographic purification of the residue afforded 5.3 g 
(77%) of product as a pale yellow sold: mp 61.degree.-62.degree. C. 
EXAMPLE J-3 
3-Pyridinecarboxylic acid, 
5-(acetylethylamino)-2-(difluoromethyl)-4-(2-methylpropyl)-6-(trifluoromet 
hyl)-, methyl ester 
A solution of 5.09 g (0.014 mol) of product of Example H-2 and 30 mL of 
acetyl chloride was stirred at room temperature for 60 h. The excess of 
acetyl chloride was evaporated, and the residue was purified by 
chromatography to afford 5.46 g (96%) of product as a colorless oil: 
n.sub.D.sup.25 =1.5855. 
EXAMPLE J-4 
3-Pyridinecarboxylic acid, 
5-(cyclopropylcarbonyl)ethylamino]-2-(difluoromethyl)-4-(2-methylpropyl)-6 
-(trifluoromethyl)-, methyl ester 
A solution of 5.09 g (0.014 mol) of product of Example H-2 and 2.23 g 
(0.021 mol) of cyclopropane carboxylic acid chloride in 50 mL of benzene 
was heated at reflux for 72 h. The benzene was evaporated, and the residue 
was purified by chromatography to afford 5.35 g (90%) of product as a pale 
yellow oil: n.sub.D.sup.25 =1.5851. 
EXAMPLE J-5 
3-Pyridinecarboxylic acid, 
6-(difluoromethyl)-5-(formylmethylamino)-4-(2-methylpropyl)-2-(trifluorome 
thyl)-, methyl ester 
To a solution of 7.08 g (0.02 mol) of product of Example G-3 in 20 mL of 
dry THF at -78.degree. C. was added 20 mL (0.02 mol) of 1M sodium 
bis(trimethylsilyl)amide in THF. After 1 h, 14.2 g (0.1 mol) of methyl 
iodide was added and the mixture was slowly warmed to room temperature 
over 1 h. After stirring for 12 h at room temperature, 25 mL of saturated 
ammonium chloride solution was added and the mixture was extracted with 
ethyl acetate (3.times.100 mL). The combined organic layers were washed 
with water, dried (MgSO.sub.4), and evaporated. Chromatographic 
purification of the residue afforded 5.6 g (76%) of product as a pale 
yellow solid: mp 85.degree.-86.degree. C. 
PREATION OF DIALKYLAMINO PYRIDINE COMPOUNDS OF THIS INVENTION 
EXAMPLE 1 
3-Pyridinecarboxylic acid, 
5-[(cyclopropylmethyl)methylamino]-2-(difluoromethyl)-4-(2-methylpropyl)-6 
-(trifluoromethyl)-, methyl ester 
To a solution of 3.26 g (0.008 mol) of product of Example J-1 in 20 mL of 
dry THF was added dropwise 10 mL (0.02 mol) of 2M borane-methyl sulfide in 
THF. The mixture was then heated at reflux for 8 h. The reaction was 
quenched by cautiously adding 5 mL of methanol while cooling in ice bath. 
After the frothing ceased, 10 mL of conc. HCl was added and the mixture 
was heated at reflux for 1 h. After cooling to room temperature, the 
solvent was evaporated and the residue was partitioned between 100 mL of 
ethyl acetate and 100 mL of 10% sodium hydroxide solution. The organic 
layer was washed with water, dried (MgSO.sub.4), and evaporated. 
Purification of the residue by chromatography followed by kugelrohr 
distillation (1.5 torr, 115.degree.-120.degree. C.) afforded 1.8 g (57%) 
of title compound as a pale yellow oil: n.sub.D.sup.25 =1.5925. 
The following Examples 2 to 5 were prepared according to the procedure used 
in Example 1. 
EXAMPLE 2 
3-Pyridinecarboxylic acid, 
2-(difluoromethyl)-5-(ethylmethylamino)-4-(2-methylpropyl)-6-(trifluoromet 
hyl)-, methyl ester 
70% yield from product of Example J-2 as a pale yellow liquid: 
n.sub.D.sup.25 =1.6175. 
EXAMPLE 3 
3-Pyridinecarboxylic acid, 
5-(diethylamino)-2-(difluoromethyl)-4-(2-methylpropyl)-6-(trifluoromethyl) 
-, methyl ester 
22% yield from product of Example J-3 as a pale yellow liquid: 
n.sub.D.sup.25 =1.5866. 
EXAMPLE 4 
3-Pyridinecarboxylic acid, 
5-[(cyclopropylmethyl)ethylamino]-2-(difluoromethyl)-4-(2-methylpropyl)-6- 
(trifluoromethyl)-, methyl ester 
19% yield from product of Example J-4 as a colorless oil: n.sub.D.sup.25 
=1.5840. 
EXAMPLE 5 
3-Pyridinecarboxylic acid, 
6-(difluoromethyl)-5-(dimethylamino)-4-(2-methylpropyl)-2-(trifluoromethyl 
)-, methyl ester 
60% yield from product of Example J-5 as a pale yellow liquid: 
n.sub.D.sup.25 =1.6120. 
EXAMPLE 6 
3-Pyridinecarbothioic acid, 
6-(difluoromethyl)-5-(dimethylamino)-4-(2-methylpropyl)-2-(trifluoromethyl 
)-, S-methyl ester 
To a solution of 5 g (0.0135 mol) of product of Example G-4 in 25 mL of dry 
THF at -78.degree. C. was added 13.5 mL (0.0135 mol) of 1M sodium 
bis(trimethylsilyl)amide in THF. After 1 h, 10 mL of methyl iodide was 
added and the mixture was slowly warmed to room temperature. After 
stirring overnight, 25 mL of saturated ammonium chloride solution was 
added and the mixture was extracted with ethyl acetate (3.times.100 mL). 
The combined organic layers were washed with water, dried (MgSO.sub.4), 
and evaporated. 
To a stirred solution of the residue from above in 10 mL of dry THF was 
added 15 mL (0.03 mol) of 2M borane-methyl sulfide in THF. The mixture was 
heated at reflux for 4 h, and then cooled in ice bath while 10 mL of 
methanol was added cautiously. After frothing had ceased, 10 mL of conc. 
HCl was added and the mixture was heated at reflux for 1 h. The reaction 
was cooled to room temperature, the solvent was removed by evaporation 
under reduced pressure, and the residue was partitioned between ethyl 
acetate (100 mL) and 10% sodium hydroxide solution (100 mL). The organic 
layer was washed with water, dried (MgSO.sub.4) and evaporated. Kugelrohr 
distillation (0.7 torr, 120.degree.-122.degree. C.) of the residue 
afforded 3.3 g (66%) of product as a pale yellow oil: n.sub.D.sup.25 
=1.6035. 
The following compounds of Examples 7 and 8 were prepared in a manner 
similar to that of Example 6. 
EXAMPLE 7 
3-Pyridinecarboxylic acid, 
2-(difluoromethyl)-5-(dimethylamino)-4-(2-methylpropyl)-6-(trifluoromethyl 
)-, methyl ester 
61% yield from product of Example G-1 as a pale yellow liquid: 
n.sub.D.sup.25 =1.6020. 
EXAMPLE 8 
3-Pyridinecarboxylic acid, 
4-(cyclopropylmethyl)-2-(difluoromethyl)-5-(dimethylamino)-6-(trifluoromet 
hyl)-, methyl ester 
55% yield from product of Example G-5 as a yellow liquid: n.sub.D.sup.25 
=1.5934. 
EXAMPLE 9 
3-Pyridinecarboxylic acid, 
4-(cyclopropylmethyl)-2-(difluoromethyl)-5-(ethylmethylamino)-6-(trifluoro 
methyl)-, methyl ester 
To a solution of 4.05 g (0.0115 mol) of product of Example G-5 in 25 mL of 
dry THF at -78.degree. C. was added 11.5 mL (0.0115 mol) of 1M sodium 
bis(trimethylsilyl)amide in THF. After 1 h, 10 mL of ethyl iodide was 
added and the mixture was slowly warmed to room temperature. The solution 
was then heated at reflux for 10 h. After cooling to room temperature, 25 
mL of saturated ammonium chloride solution was added and the mixture was 
extracted with ethyl acetate (3.times.100 mL). The combined organic layers 
were washed with water, dried (MgSO.sub.4), and evaporated. 
To a stirred solution of the residue from above in 10 mL of dry THF was 
added 15 mL (0.03 mol) of 2M borane-methyl sulfide in THF. The mixture was 
heated at reflux for 4 h, and then cooled in ice bath while 10 mL of 
methanol was added cautiously. After frothing had ceased, 10 mL of conc. 
HCl was added and the mixture was heated at reflux for 1 h. The reaction 
was cooled to room temperature, the solvent was removed by evaporation 
under reduced pressure, and the residue was partitioned between ethyl 
acetate (100 mL) and 10% sodium hydroxide solution (100 mL). The organic 
layer was washed with water, dried (MgSO.sub.4), and evaporated. kugelrohr 
distillation (0.7 torr, 123.degree.-125.degree. C.) of the residue 
afforded 2.46 g (58%) of product as a pale yellow liquid: n.sub.D.sup.25 
=1.6030. 
EXAMPLE 10 
3-Pyridinecarboxylic acid, 
5-[(2-aminoethyl)methylamino)-2-(difluoromethyl)-4-(2-methylpropyl]-6-(tri 
fluoromethyl)-, methyl ester 
To a solution of 3.54 g (0.01 mol) of product of Example G-1 in 20 mL of 
dry THF at -78.degree. C. was added 10 mL (0.01 mol) of 1M sodium 
bis(trimethylsilyl)amide in THF. After 1 h, a solution of 1.2 g (0.01 mol) 
of bromoacetonitrile in 5 mL of THF was added and the mixture was slowly 
warmed to room temperature. After 12 h, the reaction was quenched by the 
addition of 10 mL of saturated ammonium chloride solution. The mixture was 
diluted with water and extracted with ethyl acetate (3.times.100 mL). The 
combined organic layers were washed with water, dried (MgSO.sub.4), and 
evaporated to obtain a yellow orange oil. 
To a stirred solution of the crude product from above in 50 mL of dry THF 
was added 12 mL (0.024 mol) of 2M borane-methyl sulfide in THF. The 
mixture was heated at reflux for 5 h, and then cooled in ice bath while 10 
mL of methanol was added cautiously. After frothing had ceased, 10 mL of 
conc. HCl was added and the mixture was heated at reflux for 1 h. The 
reaction was cooled to room temperature, the solvent was removed by 
evaporation under reduced pressure, and the residue was partitioned 
between ethyl acetate (100 mL) and 10% sodium hydroxide solution (100 mL). 
The organic layer was washed with water, dried (MgSO.sub.4), and 
evaporated. Chromatographic purification of the residue on chromatotron 
afforded 0.8 g (21%) of title compound as a pale yellow oil: 
n.sub.D.sup.25 =1.5825. 
EXAMPLE 11 
3-Pyridinecarboxylic acid, 
2-(difluoromethyl)-5-[(2-hydroxyethyl)methylamino]-4-(2-methylpropyl)-6-(t 
rifluoromethyl)-, methyl ester 
To a stirred solution of 7.08 g (0.02 mol) of product of Example G-1 in 50 
mL of dry THF at -78.degree. C. was added 20 mL (0.02 mol) of 1M sodium 
bis(trimethylsilyl)amide in THF. After 1 h at -78.degree. C., a solution 
of 3.06 g (0.02 mol) of methyl bromoacetate in 5 mL of THF was added and 
the mixture was slowly warmed to room temperature. After 48 h, the 
reaction was quenched by the addition of 10 mL of saturated ammonium 
chloride solution. The mixture was diluted with water and extracted with 
ethyl acetate (3.times.100 mL). The combined organic layers were washed 
with water, dried (MgSO.sub.4), and evaporated to obtain a yellow oil. 
To a stirred solution of the crude product from above in 50 mL of dry THF 
was added 25 mL (0.05 mol) of 2M borane-methyl sulfide in THF. The mixture 
was heated at reflux for 8 h, and then cooled in ice bath while 20 mL of 
methanol was added cautiously. After frothing had ceased, 20 mL of conc. 
HCl was added and the mixture was heated at reflux for 1 h. The reaction 
was cooled to room temperature, the solvent was removed by evaporation 
under reduced pressure, and the residue was partitioned between ethyl 
acetate (100 mL) and 10% sodium hydroxide solution (100 mL). The organic 
layer was washed with water, dried (MgSO.sub.4), and evaporated. 
Chromatographic purification of the residue on chromatotron afforded 3.6 g 
(47%) of this Example as a yellow oil: n.sub.D.sup.25 =1.5870. 
EXAMPLE 12 
3-Pyridinecarboxylic acid, 
2-(difluoromethyl)-4-(2-methylpropyl)-5-(methylpropylamino)-6-(trifluorome 
thyl), methyl ester 
A solution of 3.88 g (0.00114 mol) of product of Example G-1 in 25 mL of 
propionyl chloride was allowed to stand at room temperature overnight. 
Excess propionyl chloride was removed by evaporation under reduced 
pressure and the residue was used in the next step without further 
purification. 
To a solution of the above residue in 15 mL of dry THF at 0.degree. C. was 
added 12 mL (0.024 mol) of 2M borane-methyl sulfide in THF and the mixture 
was heated at reflux overnight. The reaction was then cooled to 0.degree. 
C. and 10 mL of methanol was added. After the frothing ceased, 10 mL conc. 
HCl was added and the mixture was heated at reflux for 1 h. The reaction 
mixture was evaporated under reduced pressure and the residue was 
partitioned between 100 mL of ethyl acetate and 50 mL of 10% sodium 
hydroxide solution. The organic layer was washed with water, dried 
(MgSO.sub.4), and evaporated. Chromatographic purification of the residue 
on chromatotron afforded 2.65 g (61%) of product as a pale yellow oil: 
n.sub.D.sup.25 =1.5829. 
PRE-EMERGENCE HERBICIDE EXAMPLES 
As noted above, the compounds of this invention have been found to be 
surprisingly effective as herbicides, particularly pre-emergence 
herbicides. 
The tests for pre-emergence herbicide activity are conducted as follows: 
Topsoil is placed in an aluminum pan and compacted to a depth of 0.95 to 
1.27 cm. from the top of the pan. On the top of the soil is placed a 
predetermined number of seeds of each of several monocotyledonous and 
dicotyledonous annual plant species and/or vegetative propagules of 
various perennial plant species. The soil required to level fill a pan 
after seeding or adding vegetative propagules is weighed into another pan. 
A known amount of the active ingredient dissolved or suspended in an 
organic solvent or water and applied in acetone or water as a carrier is 
thoroughly mixed with this cover soil, and the herbicide/soil mixture is 
used as a cover layer for the previously prepared pan. In Table 1 below 
the for example, amount of active ingredient applied in the cover layer 
soil is equal to an application rate of 11.2 kg/ha. After treatment, the 
pans are moved to a greenhouse bench where they are watered from below as 
needed to give adequate moisture for germination and growth. 
Approximately 10-14 days (usually 11 days) after seeding and treating, the 
pans are observed and the results (% inhibition) are recorded. 
Table 1 below summarizes the results of the pre-emergence herbicidal 
activity tests of compounds of this invention in weeds. The herbicidal 
rating shown in Table 1 is the percent inhibition of each plant species 
according to the following rating system: 
______________________________________ 
Plant Response Index 
______________________________________ 
0-24% inhibition 0 
25-49% inhibition 1 
50-74% inhibition 2 
75-100% inhibition 3 
Species not planted 
-- 
Species planted, no data 
N 
______________________________________ 
The plant species usually regarded as weeds which are utilized in one set 
of tests, the data for which are shown in Table 1, are identified by 
letter headings above the columns in accordance with the following legend: 
Yens--Yellow nutsedge 
Anbg--Annual bluegrass 
Sejg--Seedling johnsongrass 
Dobr--Downy Brome 
Bygr--Barnyardgrass 
Mogl--Morningglory 
Cobu--Cocklebur 
Vele--Velvetleaf 
Inmu--Indian mustard 
Wibw--Wild buckwheat 
Cath--Canada thistle 
Colq--Common lambsquarters 
Pesw--Pennsylvania smartweed 
Rhqg--Rhizome quackgrass 
Rhjg--Rhizome johnsongrass 
TABLE 1 
__________________________________________________________________________ 
PRE-EMERGENCE HERBICIDE DATA 
Ex. 
Rate 
No. 
kg/ha 
Yens 
Anbg 
Sejg 
Dobr 
Bygr 
Mogl 
Cobu 
Vele 
Inmu 
Wibw 
Cath 
Colq 
Pesw 
Rhqg 
Rhjg 
__________________________________________________________________________ 
1 11.21 
1 3 3 3 3 3 3 3 3 3 
2 11.21 
3 3 3 3 3 3 3 3 3 3 3 
3 11.21 
1 3 3 3 3 3 0 3 3 3 
4 11.21 
2 3 3 3 3 2 0 3 3 3 
5 11.21 
0 3 3 3 1 2 2 3 1 3 -- 
6 11.21 
0 3 3 3 1 2 2 3 3 3 -- 
7 11.21 
3 3 3 3 3 3 3 3 3 3 3 
8 11.21 
3 3 3 3 3 3 3 3 3 3 3 
9 11.21 
3 3 3 3 3 3 3 3 3 3 -- 
10 11.21 
0 0 1 0 0 0 0 0 N 0 0 
11 11.21 
0 3 3 3 3 3 3 3 3 3 
12* 
11.21 
2 3 3 3 3 3 3 3 3 3 
__________________________________________________________________________ 
*DAMPING OFFINMU AND WIBW; POOR GERMINATIONCOBU 
POST-EMERGENCE HERBICIDE EXAMPLES 
The post-emergence herbicidal activity of some of the various compounds of 
this invention was demonstrated by greenhouse testing in the following 
manner. Topsoil is placed in aluminum pans having holes in the bottom and 
compacted to a depth of 0.95 to 1.27 cm. from the top of the pan. A 
predetermined number of seeds of each of several dicotyledonous and 
monocotyledonous annual plant species and/or vegetative propagules for the 
perennial plant species are placed on the soil and pressed into the soil 
surface. The seeds and/or vegetative propagules are covered with soil and 
leveled. The pans are then placed on a bench in the greenhouse and watered 
from below as needed. After the plants reach the desired age (two to three 
weeks), each pan, is removed individually to a spraying chamber and 
sprayed by means of an atomizer, operating at a spray pressure of 170.3 
kPa (10 psig) at the application rates noted. In the spray solution is an 
amount of an emulsifying agent mixture to give a spray solution or 
suspension which contains about 0.4% by volume of the emulsifier. The 
spray solution or suspension contains a sufficient amount of the active 
chemical in order to give application rates of the active ingredient 
corresponding to those shown in the Tables while applying a total amount 
of solution or suspension equivalent to 1870 L/Ha (200 gallons/acre). The 
pans were returned to the greenhouse and watered as before and the injury 
to the plants as compared to the control is observed at approximately 
10-14 days (usually 11 days) and in some instances observed again at 24-28 
days (usually 25 days) after spraying. The post-emergent herbicidal 
activity index used in Table 2 is as follows: 
______________________________________ 
Plant Response Index 
______________________________________ 
0-24% inhibition 0 
25-49% inhibition 1 
50-74% inhibition 2 
75-99% inhibition 3 
100% inhibition 4 
Species not planted 
-- 
Species planted, no data 
N 
______________________________________ 
TABLE 2 
__________________________________________________________________________ 
POST-EMERGENCE HERBICIDE DATA 
Ex. 
Rate 
No. 
kg/ha 
Yens 
Anbg 
Sejg 
Dobr 
Bygr 
Mogl 
Cobu 
Vele 
Inmu 
Wibw 
Cath 
Colq 
Pesw 
Rhqg 
Rhjg 
__________________________________________________________________________ 
1 11.21 
0 0 1 0 0 1 0 1 2 2 
2 11.21 
0 0 0 0 0 0 0 0 0 0 N 
3 11.21 
0 2 2 0 2 0 0 2 0 0 
4 11.21 
0 0 2 0 0 1 2 2 0 2 
5 11.21 
0 0 0 0 0 0 0 0 0 0 0 
6 11.21 
0 0 0 1 0 0 0 0 0 0 0 
7 11.21 
0 0 2 1 0 1 -- 1 0 0 N 
8 11.21 
0 0 1 1 0 0 0 2 0 0 0 
9 11.21 
0 0 2 1 1 1 1 N 0 0 0 
10 11.21 
0 0 0 0 0 0 0 0 N 0 0 
11 11.21 
0 0 0 0 1 0 0 2 1 2 
12* 
11.21 
0 2 2 0 2 2 1 2 2 2 
__________________________________________________________________________ 
*DAMPING OFFINMU AND WIBW; POOR GERMINATIONCOBU 
PRE-EMERGENCE CROP AND WEED PLANT HERBICIDE ACTIVITY 
The compounds of this invention were further tested by utilizing the above 
procedure for pre-emergence testing on the following plant species, i.e., 
on weeds in the presence of crop plants. The following plant species were 
used in these tests. 
______________________________________ 
Sobe - Soybean Colq - Common lambsquarters 
Sube - Sugarbeet Pesw - Pennsylvania smartweed 
Whez - Wheat Vele - Velvetleaf 
Rice - Rice Dobr - Downy brome 
Grso - Grain sorghum 
Rape - Oilseed rape 
Cobu - Cocklebur Bygr - Barnyardgrass 
Wibw - Wild buckwheat 
Lacg - Large crabgrass 
Mogl - Morningglory 
Grft - Green foxtail 
Hese - Hemp sesbania 
Corn - Corn 
Cotz - Cotton Prmi - Proso millet 
Jiwe - Jimsonweed 
______________________________________ 
The results of these tests are summarized in Table 3 below, in which the 
rating codes are the same as those used in Table 1. 
3 TABLE 3 
Ex. Rate No. kg/ha Sobe Cotz Rape Cobu Wibw Mogl 
Hese Jiwe Vele Whez Rice Grso Corn Dobr Prmi Bygr Lacg Grft Sube Colq 
Pesw 
1 5.6050 3 2 3 1 3 3 3 3 3 3 3 3 3 3 3 3 3 3 1.1210 2 0 2 1 3 2 3 
2 2 3 3 3 3 3 3 3 3 3 0.2803 1 0 0 0 0 0 0 0 0 1 0 3 1 3 0 1 3 2 
0.0701 0 0 0 1 0 N 0 0 0 0 0 0 0 0 0 0 0 0 0.0175 0 0 0 0 0 0 N 0 N 0 0 
N 1 0 0 0 0 0 2 5.6050 3 1 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 1.1210 3 
0 2 3 2 1 3 3 3 3 3 3 3 3 3 3 3 3 0.5605 3 3 0 3 1 0 3 3 3 3 3 3 3 
3 3 3 3 3 0.2803 3 1 0 3 0 0 3 3 3 3 1 3 3 3 3 0 1 2 0.1401 1 0 1 
0 0 0 3 0 3 0 3 1 3 3 3 1 2 1 0.0701 0 0 N 0 0 0 1 N 2 0 3 N 3 3 3 
1 N 0 0.0350 N N 0 N 0 0 0 0 1 0 2 1 2 0 3 0 1 0 0.0175 0 0 0 0 0 
0 0 0 0 0 0 0 0 0 0 0 N 1 0.0087 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 
0 0.0044 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 3 5.6050 3 1 3 2 3 3 3 
3 3 3 3 3 3 3 3 3 3 3 1.1210 0 1 0 0 3 1 1 2 1 3 3 3 3 3 3 3 3 3 
0.2803 1 1 0 0 0 0 0 0 0 1 1 3 2 2 3 3 3 3 0.0701 0 0 0 0 0 0 0 1 0 0 0 
0 0 2 1 0 1 1 0.0175 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 4 5.6050 2 1 3 
3 3 2 2 3 3 3 3 3 3 3 3 3 3 3 1.1210 0 1 2 0 3 1 1 3 1 3 3 3 2 3 3 3 3 
3 0.2803 0 0 0 0 2 0 0 1 0 0 0 1 0 3 2 3 3 3 0.0701 0 N 0 0 0 0 0 1 0 
0 0 0 0 0 1 0 3 1 0.0175 0 1 0 1 1 1 0 1 0 0 0 0 N 0 0 0 1 0 0.0087 0 
0 0 0 1 0 0 3 0 0 0 0 0 N 1 0 N 0 5 5.6050 3 0 1 3 1 2 3 3 3 3 3 3 3 
3 3 3 3 3 1.1210 0 0 0 1 0 0 1 3 0 0 3 3 3 3 3 0 1 1 0.5605 0 0 0 
1 0 0 N 2 0 0 0 0 0 2 0 0 0 0 0.2803 0 1 0 0 0 0 0 0 0 0 1 0 0 1 0 
1 1 1 0.1401 1 0 0 0 0 0 0 0 1 0 0 0 0 1 1 0 0 0 0.0701 N 0 0 0 0 
0 0 0 0 1 0 1 0 2 0 N 1 1 0.0350 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 
1 0.0175 0 1 1 0 0 0 0 0 N 1 0 0 0 0 0 0 1 1 6 5.6050 3 0 3 3 2 2 
3 3 3 3 3 3 3 3 3 3 3 3 1.1210 1 1 0 3 0 1 3 3 1 1 3 3 3 3 2 1 2 2 
0.5605 0 3 0 0 0 0 1 3 0 0 2 3 0 3 0 0 1 1 0.2803 0 0 0 0 0 0 N 0 
0 0 0 0 0 0 0 1 0 N 0.1401 0 0 0 0 0 0 2 0 0 0 0 0 0 1 0 0 1 0 
0.0701 0 0 0 0 0 0 1 0 0 0 0 N 0 N 0 0 0 0 0.0350 0 0 N 0 0 0 2 0 
0 0 0 0 0 0 0 0 N 0 0.0175 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0 
0.0087 N 0 0 0 0 0 N 0 0 0 0 0 0 N 0 0 N 0 7 5.6050 3 2 3 2 3 3 3 
3 3 3 3 3 3 3 3 3 3 3 1.1210 2 0 1 3 3 3 3 3 3 2 3 3 3 3 3 3 3 3 
0.5605 2 1 0 3 1 1 3 3 3 1 3 3 3 3 3 3 3 3 0.2803 0 0 0 0 2 0 3 3 
1 0 3 3 3 3 3 3 0 1 0.1401 0 0 0 0 1 0 1 3 0 0 1 3 3 1 3 1 0 1 
0.0701 0 0 0 0 0 0 0 0 0 0 0 2 0 2 3 0 0 0 0.0350 0 0 0 0 0 0 0 0 
0 0 0 0 0 0 1 0 0 0 0.0175 0 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 
0.0087 0 0 0 0 0 0 0 0 0 0 0 N 0 0 0 N N N 0.0044 0 0 0 0 0 0 0 0 
0 0 0 0 0 0 0 0 0 0 8 5.6050 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 
1.1210 3 1 0 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 0.5605 2 1 0 3 0 0 3 3 
3 3 3 3 3 3 3 3 3 3 0.2803 2 1 0 1 0 0 3 3 3 1 3 3 3 3 3 2 2 1 
0.1401 0 2 0 0 0 0 2 0 3 1 3 2 3 3 3 1 0 2 0.0701 1 1 0 1 0 0 3 1 
3 0 2 N 3 3 3 1 0 1 0.0350 0 0 0 0 0 0 0 0 1 0 0 1 3 1 3 0 0 2 
0.0175 0 0 0 0 0 0 0 0 1 0 0 0 3 0 3 0 1 0 0.0087 N 0 0 0 0 0 0 0 
0 0 0 0 2 0 3 0 0 0 0.0044 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 1 9 
5.6050 3 2 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 1.1210 2 3 3 3 3 3 3 3 
3 3 3 3 3 3 3 3 3 3 0.5605 1 1 2 3 2 3 3 3 3 3 3 3 3 3 3 3 3 3 
0.2803 1 0 0 2 1 0 3 3 3 1 3 3 3 3 3 0 0 2 0.1401 1 0 0 1 0 0 3 3 
2 0 3 3 3 3 3 1 1 1 0.0701 0 0 1 0 0 0 2 3 3 0 3 3 3 3 3 0 0 0 
0.0350 1 0 1 0 0 0 0 0 0 0 0 0 3 3 3 0 0 0 0.0175 0 0 N 0 0 0 0 0 
0 0 0 0 3 3 3 0 0 1 0.0087 0 0 N 0 1 0 0 0 0 0 N 0 1 3 2 0 N 1 
0.0044 0 0 1 0 0 0 0 0 0 0 0 1 0 2 0 0 N 1 11 5.6050 3 1 2 2 3 3 2 3 
3 3 3 3 3 3 3 3 3 3 1.1210 0 0 1 0 2 0 0 1 0 3 1 3 2 3 3 3 3 2 0.2803 
1 0 0 0 0 0 0 0 0 1 0 2 1 1 0 0 0 3 0.0701 0 0 0 0 0 0 0 0 0 1 0 1 0 0 
0 0 0 0 0.0175 0 N 0 0 0 0 0 N 1 1 0 1 0 0 0 0 0 0 12 5.6050 3 3 3 1 3 
3 3 3 3 3 3 3 3 3 3 3 3 3 1.1210 3 1 3 2 1 2 2 1 1 3 3 3 3 3 3 3 3 3 
0.2803 1 0 0 0 0 0 0 0 1 3 1 3 1 3 3 3 3 3 0.0701 0 0 0 0 0 0 0 0 0 0 1 
0 0 0 1 1 3 3 0.0175 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0.0087 0 0 0 
0 0 0 0 0 0 0 0 0 0 0 0 0 N 0 
The herbicidal compositions of this invention, including concentrates which 
require dilution prior to application, may contain at least one active 
ingredient and an adjuvant in liquid or solid form. The compositions are 
prepared by admixing the active ingredient with an adjuvant including 
diluents, extenders, carriers, and conditioning agents to provide 
compositions in the form of finely-divided particulate solids, granules, 
pellets, solutions, dispersions or emulsions. Thus, it is believed that 
the active ingredient could be used with an adjuvant such as a 
finely-divided solid, a liquid of organic origin, water, a wetting agent, 
a dispersing agent, an emulsifying agent or any suitable combination of 
these. 
Suitable wetting agents are believed to include alkyl benzene and alkyl 
naphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, 
long chain acid esters of sodium isothionate, esters of sodium 
sulfosuccinate, sulfated or sulfonated fatty acid esters, petroleum 
sulfonates, sulfonated vegetable oils, ditertiary acetylenic glycols, 
polyoxyethylene derivatives of alkylphenols (particularly isooctylphenol 
and nonylphenol) and polyoxyethylene derivatives of the mono-higher fatty 
acid esters of hexitol anhydrides (e.g., sorbitan). Preferred dispersants 
are methyl cellulose, polyvinyl alcohol, sodium lignin sulfonates, 
polymeric alkyl naphthalene sulfonates, sodium naphthalene sulfonate, and 
polymethylene bisnaphthalene sulfonate. Wettable powders are 
water-dispersible compositions containing one or more active ingredients, 
an inert solid extender and one or more wetting and dispersing agents. The 
inert solid extenders are usually of mineral origin such as the natural 
clays, diatomaceous earth and synthetic minerals derived from silica and 
the like. Examples of such extenders include kaolinites, attapulgite clay 
and synthetic magnesium silicate. The wettable powders compositions of 
this invention usually contain from above 0.5 to 60 parts (preferably from 
5-20 parts) of active ingredient, from about 0.25 to 25 parts (preferably 
1-15 parts) of wetting agent, from about 0.25 to 25 parts (preferably 
1.0-15 parts) of dispersant and from 5 to about 95 parts (preferably 5-50 
parts) of inert solid extender, all parts being by weight of the total 
composition. Where required, from about 0.1 to 2.0 parts of the solid 
inert extender can be replaced by a corrosion inhibitor or anti-foaming 
agent or both. 
Other formulations include dust concentrates comprising from 0.1 to 60% by 
weight of the active ingredient on a suitable extender; these dusts may be 
diluted for application at concentrations within the range of from about 
0.1-10% by weight. 
Aqueous suspensions or emulsions may be prepared by stirring a nonaqueous 
solution of a water-insoluble active ingredient and an emulsification 
agent with water until uniform and then homogenizing to give stable 
emulsion of very finely divided particles. The resulting concentrated 
aqueous suspension is characterized by its extremely small particle size, 
so that when diluted and sprayed, coverage is very uniform. Suitable 
concentrations of these formulations contain from about 0.1-60% preferably 
5-50% by weight of active ingredient, the upper limit being determined by 
the solubility limit of active ingredient in the solvent. 
Concentrates are usually solutions of active ingredient in water-immiscible 
or partially water-immiscible solvents together with a surface active 
agent. Suitable solvents for the active ingredient of this invention 
include dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, 
hydrocarbons, and water-immiscible ethers, esters, or ketones. However, 
other high strength liquid concentrates may be formulated by dissolving 
the active ingredient in a solvent then diluting, e.g., with kerosene, to 
spray concentration. 
The concentrate compositions herein generally contain from about 0.1 to 95 
parts (preferably 5-60 parts) active ingredient, about 0.25 to 50 parts 
(preferably 1-25 parts) surface active agent and where required about 4 to 
94 parts solvent, all parts being by weight based on the total weight of 
emulsifiable oil. 
Granules are physically stable particulate compositions comprising active 
ingredient adhering to or distributed through a basic matrix of an inert, 
finely-divided particulate extender. In order to aid leaching of the 
active ingredient from the particulate extender, a surface active agent 
such as those listed hereinbefore can be present in the composition. 
Natural clays, pyrophyllites, illite, and vermiculite are examples of 
operable classes of particulate mineral extenders. The preferred extenders 
are the porous, absorptive, preformed particles such as preformed and 
screened particulate attapulgite or heat expanded, particulate vermiculite 
and the finely-divided clays such as kaolin clays, hydrated attapulgite or 
bentonitic clays. These extenders are sprayed or blended with the active 
ingredient to form the herbicidal granules. 
The granular compositions of this invention may contain from about 0.1 to 
about 30 parts by weight of active ingredient per 100 parts by weight of 
clay and 0 to about 5 parts by weight of surface active agent per 100 
parts by weight of particulate clay. 
The compositions of this invention can also contain other additaments, for 
example, fertilizers, other herbicides, other pesticides, safeners and the 
like used as adjuvants or in combination with any of the above-described 
adjuvants. Chemicals useful in combination with the active ingredients of 
this invention included, for example, triazines, ureas, carbamates, 
acetamides, acetanilides, uracils, acetic acid or phenol derivatives, 
thiolcarbamates, triazoles, benzoic acids, nitriles, biphenyl ethers and 
the like such as: 
Hetetocyclic Nitrogen/Sulfur Derivatives 
2-Chloro-4-ethylamino-6-isopropylamino-s-triazine 
2-Chloro-4,6-bis(isopropylamino)-s-triazine 
2-Chloro-4,6-bis(ethylamino)-s-triazine 
3-Isopropyl-1H-2,1,3-benzothiadiazin-4-(3H)-one 2,2-dioxide 
3-Amino-1,2,4-triazole 
6,7-Dihydrodipyrido(1,2-:2',1'-c)-pyrazidiinium salt 
5-Bromo-3-isopropyl-6-methyluracil 
1,1'-Dimethyl-4,4'-bipyridinium 
2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-3-quinolinecarboxylic acid 
Isopropylamine salt of 
2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid 
Methyl 6-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-m-toluate and 
methyl 2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-p-toluate 
Ureas 
N-(4-chlorophenoxy) phenyl-N,N-dimethylurea 
N,N-dimethyl-N'-(3-chloro-4-methylphenyl) urea 
3-(3,4-dichlorophenyl)-1,1-dimethylurea 
1,3-Dimethyl-3-(2-benzothiazolyl) urea 
3-(p-Chlorophenyl)-1,1-dimethylurea 
1-Butyl-3-(3,4-dichlorophenyl)-1-methylurea 
2-Chloro-N[(4-methoxy-6-methyl-1,3,5-triazin-2-yl) 
aminocarbonyl]-benzenesulfonamide 
Methyl 2-(((((4,6-dimethyl-2-pyrimidinyl)amino)carbonyl)amino)sulfonyl) 
benzoate 
Ethyl 2-[methyl 
2-(((((4,6-dimethyl-2-pyrimidinyl)amino)carbonyl)amino)sulfonyl)] benzoate 
Methyl-2((4,6-dimethoxy pyrimidin-2-yl)aminocarbonyl)amino sulfonyl methyl) 
benzoate 
Methyl 
2-(((((4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino)carbonyl)amino)sulfonyl 
) benzoate 
Carbamates/Thiolcarbamates 
2-Chloroallyl diethyldithiocarbamate 
S-(4-chlorobenzyl)N,N-diethylthiolcarbamate 
Isopropyl N-(3-chlorophenyl)carbamate 
S-2,3-dichloroallyl N,N-diisopropylthiolcarbamate 
S-N,N-dipropylthiolcarbamate 
S-propyl N,N-dipropylthiolcarbamate 
S-2,3,3-trichloroallyl-N,N-diisopropylthiolcarbamate 
Acetamides/Acetanilides/Anilines/Amides 
2-Chloro-N,N-diallylacetamide 
N,N-dimethyl-2,2-diphenylacetamide 
N-(2,4-dimethyl-5-[[[(trifluoromethyl)sulfonyl]amino]phenyl]acetamide 
N-Isopropyl-2-chloroacetanilide 
2',6'-Diethyl-N-methoxymethyl-2-chloroacetanilide 
2'-Methyl-6'-ethyl-N-(2-methoxyprop-2-yl)-2-chloroacetanilide 
.alpha.,.alpha.,.alpha.-Trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine 
N-(1,1-dimethylpropynyl)-3,5-dichlorobenzamide 
Acids/Esters/Alcohols 
2,2-Dichloropropionic acid 
2-Methyl-4-chlorophenoxyacetic acid 
2,4-Dichlorophenoxyacetic acid 
Methyl-2-[4-(2,4-dichlorophenoxy)phenoxy]propionate 
3-Amino-2,5-dichlorobenzoic acid 
2-Methoxy-3,6-dichlorobenzoic acid 
2,3,6-Trichlorophenylacetic acid 
N-1-naphthylphthalamic acid 
Sodium 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate 
4,6-Dinitro-o-sec-butylphenol 
N-(phosphonomethyl)glycine and its salts. 
Butyl (R)-2-[4-[(5-(trifluoromethyl)-2-pyridinyl)oxy]phenoxy]-propanoate 
Ethers 
2,4-Dichlorophenyl-4-nitrophenyl ether 
2-Chloro-.delta.,.delta.,.delta.-trifluoro-p-tolyl-3-ethoxy-4-nitrodiphenyl 
ether 
5-(2-chloro-4-trifluoromethylphenoxy)-N-methylsulfonyl 2-nitrobenzamide 
1'-(Carboethoxy) ethyl 
5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate 
Miscellaneous 
2,6-Dichlorobenzonitrile 
Monosodium acid methanearsonate 
Disodium methanearsonate 
2-(2-chlorophenyl)methyl-4,4-dimethyl-3-isoxazolidinone 
7-oxabicyclo(2.2.1)heptane, 
1-methyl-4-(1-methylethyl)-2-(2-methylphenylmethoxy)-,exo- 
Fertilizers useful in combination with the active ingredients include, for 
example ammonium nitrate, urea, potash and superphosphate. Other useful 
additaments include materials in which plant organisms take root and grow 
such as compost, manure, humus, sand and the like. 
Herbicidal formulations of the types described above are exemplified in 
several illustrative embodiments below. 
______________________________________ 
I. Emulsifiable Concentrates 
Weight Percent 
______________________________________ 
A. Compound of Example No. 3 
11.0 
Free acid of complex organic 
5.59 
phosphate or aromatic or 
aliphatic hydrophobe base 
(e.g., GAFAC RE-610, registered 
trademark of GAF Corp.) 
Polyoxyethylene/polyoxypropylene 
1.11 
block copolymer with butanol 
(e.g., Tergitol XH, registered 
trademark of Union Carbide Corp.) 
Phenol 5.34 
Monochlorobenzene 76.96 
100.00 
B. Compound of Example No. 11 
25.00 
Free acid of complex organic 
5.00 
phosphate of aromatic or 
aliphatic hydrophobe base 
(e.g., GAFAC RE-610) 
Polyoxyethylene/polyoxypropylene 
1.60 
block copolymer with butanol 
(e.g., Tergitol XH) 
Phenol 4.75 
Monochlorobenzene 63.65 
100.00 
______________________________________ 
______________________________________ 
II. Flowables 
Weight Percent 
______________________________________ 
A. Compound of Example No. 12 
25.0 
Methyl cellulose 0.3 
Silica aerogel 1.5 
Sodium lignosulfonate 
3.5 
Sodium N-methyl-N-oleyl taurate 
2.0 
Water 67.7 
100.0 
B. Compound of Example No. 9 
45.0 
Methyl cellulose .3 
Silica aerogel 1.5 
Sodium lignosulfonate 
3.5 
Sodium N-methyl-N-oleyl taurate 
2.0 
Water 47.7 
100.0 
______________________________________ 
______________________________________ 
III. Wettable Powders 
Weight Percent 
______________________________________ 
A. Compound of Example No. 5 
25.0 
Sodium lignosulfonate 
3.0 
Sodium N-methyl-N-oleyl-taurate 
1.0 
Amorphous silica (synthetic) 
71.0 
100.0 
B. Compound of Example 10 
80.00 
Sodium dioctyl sulfosuccinate 
1.25 
Calcium lignosulfonate 
2.75 
Amorphous silica (synthetic) 
16.00 
100.00 
C. Compound of Example No. 6 
10.0 
Sodium lignosulfonate 
3.0 
Sodium N-methyl-N-oleyl-taurate 
1.0 
Kaolinite clay 86.0 
100.00 
______________________________________ 
______________________________________ 
IV. Dusts 
Weight Percent 
______________________________________ 
A. Compound of Example No. 7 
2.0 
Attapulgite 98.0 
100.0 
B. Compound of Example No. 4 
60.0 
Montmorillonite 40.0 
100.0 
C. Compound of Example No. 2 
30.0 
Ethylene glycol 1.0 
Bentonite 69.0 
100.0 
D. Compound of Example No. 1 
1.0 
Diatomaceous earth 
99.0 
100.0 
______________________________________ 
______________________________________ 
V. Granules 
Weight Percent 
______________________________________ 
A. Compound of Example No. 8 
15.0 
Granular attapulgite (20/40 mesh) 
85.0 
100.0 
B. Compound of Example No. 5 
30.0 
Diatomaceous earth (20/40) 
70.0 
100.0 
C. Compound of Example No. 12 
1.0 
Ethylene glycol 5.0 
Methylene blue 0.1 
Pyrophyllite 93.9 
100.0 
D. Compound of Example No. 7 
5.0 
Pyrophyllite (20/40) 95.0 
100.0 
______________________________________ 
When operating in accordance with the present invention, effective amounts 
of the compounds of this invention are applied to the soil containing the 
seeds, or vegetative propagules or may be incorporated into the soil media 
in any convenient fashion. The application of liquid and particulate solid 
compositions to the soil can be carried out by conventional methods, e.g., 
power dusters, boom and hand sprayers and spray dusters. The compositions 
can also be applied from airplanes as a dust or a spray because of their 
effectiveness at low dosages. The exact amount of active ingredient to be 
employed is dependent upon various factors, including the plant species 
and stage of development thereof, the type and condition of soil, the 
amount of rainfall and the specific compounds employed. In selective 
preemergence application or to the soil, a dosage of from about 0.02 to 
about 11.2 kg/ha, preferably from about 0.1 to about 5.60 kg/ha, is 
usually employed. Lower or higher rates may be required in some instances. 
One skilled in the art can readily determine from this specification, 
including the above examples, the optimum rate to be applied in any 
particular case. 
The term "soil" is employed in its broadest sense to be inclusive of all 
conventional "soils" as defined in Webster's New International Dictionary, 
Second Edition, Unabridged (1961). Thus, the term refers to any substance 
or medium in which vegetation may take root and grow, and includes not 
only earth but also compost, manure, muck, humus, loam, silt, mire, clay, 
sand, and the like, adapted to support plant growth. 
Although the invention is described with respect to specific modifications, 
the details thereof are not to be construed as limitations.