CA1189075A - Haloacetamidines and the herbicidal use thereof - Google Patents

Abstract

Abstract Dichloroacetamidines having the formula in which A and B are independently selected from hydrogen, fluorine, chlorine, bromine and methyl, provided that at least one of A or B is other than hydrogen;
M is hydrogen or methyl;
X is selected from the group consisting of trifluoromethyl, lower alkyl, nitro, chloro, bromo, fluoro, cyano, lower alkoxy scetyl, lower alkylthio, trifluoromethylthio, and 3,3-diloweralkyl ureido;
Y is selected from the group consisting of hydrogen, lower alkyl, chloro, fluoro, nitro, trifluoromethyl, and lower alkoxy;
Z is selected from the group consisting of hydrogen and chloro;
R1 is selected from the group consisting of hydrogen, alkyl and allyl;
R2 is selected from the group consisting of alkyl, allyl, benzyl, hydroxyalkyl, alkynyl, N-alkyl amido, alkoxyalkyl, dialkoxyalkyl, alkoxy, cyano alkyl, substituted phenyl wherein the substituent is selected from the group tri-fluoromethyl, dichloro and 3,3-dimethylureido; and R1 and R2 taken together with the nitrogen is selected from the group consisting of alkyl substituted oxazolidyl, morpholinyl, piperidinyl and pyrrolidinyl; and salts thereof;
useful as herbicides.

Description

~89~7~i HALOACETAMIDINES AND THE HEREICIDAL
USE THEREOF
-This invention relates to cert:ain novel halo-acetamidines which are useful as herbicides. More specifically, this invention relates to a novel herbicidal compound known as acetamidines, more particularly dichloroacetamidinesO
Back ound of the Invention gr Use o~ Herbicide_ An herbicide is a compound which controls or modifies plant growth, e.g., killing, retarding, defoliating, desiccating, regulating, stunting, tillering, stimulating, and dwarfing. "Plant" refers to all physical parts, including seeds, seedlings, saplings, roots, tubers, stems, stalks, ~oliage, and fruits. "Plant growth" is meant to include all phases of development from seed germination to natural or induced cessation o~ life.
1~ ~erbicides are generally used to control or eradicate weed pes~s. They ha~e gained a high degree of commercial success because it has been shown tha~ such control increases crop yield and reduces harvesting cos~s.
Herbicidal effectiveness is dependent upon several ~ariables. ~ne of these is the ~ime or growth related method of application. The most popular methods of application include: pre-plan~ incorporation into the soil;
pre-emergence surface treatment o~ seeded soil; and post-emergence treatment of the plant and soil.
The most importan~ determinant o~ herbicidal effectiveness is ~he suscep~ibility of the target weed.
Certain herbicidal compounds are phyts~oxic to some weed species but not to others.
The manufac~urer of the herbicide recommends a range of rates and conc~ntrations calculated to maximize , ~

8~

weed control. The range of rates varies from approximately 0.01 ~o 50 pounds per acre, usually from 0.1 to 2~ pounds per acre. The actual amount used depends upon several considerations including particular weed susceptibility and overall cost limitations.
Prior Art U.S. Patent 3,153,670 relates primarioy to vinyl amines. A utility disclosed ~or the vinyl amines is the prepara~ion of a~idines from primary amines. In U.S.
3,153,670 the following specific compo~lds are disclosed:
N,N-diethyl-N'-phenyl 2,2-dichloroacetamidine, N,N-diethyl-N'-tolyl 2,2-dichloroacetamidine, N,N-diethyl-N'-p-chloro-phenyl 2,2-dichloroacetamidine, N,N-diethyl-N'-p-nitro-phenyl 2,2-dichloroacetamidine, and N,N-diethyl-N'-p--ethoxy-phenyl 2,2-dichloroacetamidine. U.S. 3,153,670 generically discloses herbicidal utility for the above compounds. No specific testing or method of testing for herbi activity is set forth in the cited patent.
The J. Am. Chem. Soc. 82 902-9 (1960) discloses the compound N,N-diethyl-N'-phenyl 2,2-dichloroacetamidine.
U.S. Patent 3,576,618 discloses certain N-trichloroacetamidines having the formula ~ C-CC13 Rn These compounds are useful as herbicides. The form taken by the compounds are the aryl amino form, thereby allowing only one substituent on the aryl amino nitrogen and always a hydrogen on the amino nitrogen with the phenyl moiety. These are commonly known as "reverse" acetamidines.
Similarly, West German Of~enlegungschrift 2557651 rela~es ~o N-aryl-2,2-dihalo-acetamidine derivatives of the general formula 8~

R ~ N-C~NH
H-C-X
R X
wherein Rl, R~ and R3 are the same or dif~erent and are defined as a hydrogen, halogen atom, aliphatic moiety or R4-o- wherein R4 is aliphatic or aromatic moiety and X is a halogen a~om. These acetamidines are termed "reverse"
acPtamidines because of the tau~omeric system within the molecule. The utility is disclosed as fungicidal.
The following are a group of patents which relate to acetamidines in which the two (2) position is substituted with a non-halogenated methyl group: U.S. 3,284,289, U S.
3,487,156, U.S. 3,781,356, U.S. 3,781,357, U.S. 3,803,134 and U.S. 3,867,448.
The compounds disclosed in the above-cited U.S.
patents are taught to be useful for the control of acarids and insects, combating undesired plant growth, harmful micro-organisms, nematodes.
U.S. Patent 3,428,681 relates to N-halotrichloro-acetamidines having ~he general formula - N C--NX
~ ~ CC13 wherein X is chlorine, iodine or bromine and each R is independently selected from the group consis.ing of hydrogen, alkyl, aryl, cycloalkyl and heterocyclic. These compounds are disclosed as useful as bleaches and disinfectan~s, effecti~e as fungicidal, herbicidal and algaecidal agents.
It is recognized the amidine compounds hav~ the potential of existing in two geometrical isomeric forms, known as tautomers, in the aryl mino form ~ArN=C(NHR ] and ~he aryl amino iorm [ArNHC(=NR)R ]. Many compounds contain-ing an "amidine moiety" possess potential for tautomerism~
geometricaL isomerism and conformational change. The s "amidine moiety" refers to comyounds containing the poten-tially tautomeric system -NH-C(X)--N- in which X is C, N, 0 or S as described by Jackman, L. M. et al., J. Am. Chem.
S _ 97 (10) 2811~18. In the present application the predominant tautomer is presumed to be in the imino ~orm and the representation of ~he dichloro acetamidines will be in this form.
Description of the Inv~ntion The compounds comprising the instan~ class o compounds corresponds to the general formula ~R
Y N
~ N-C R2 X ~ A-CM
B

in which A and B are independently selec~ed ~rom the group conslsting of hydrogen, 1uorine, chlorine, bromlne and methyl, provided that at least one of A or B is other than hydroge~;
X is selected from the group consist;ng of trifluoromethyl, lower alkyl, nitro7 chloro, bromo, fluoro, cyano, lower alkoxy acetyl, lower alkylthio, trifluoromethylthio, and 3,3-diloweralkyl ureido, Y is selected from ~h~ group consisting of hydrogen, lower alkyl, chloro, 1uoro, nitro, trifluoromethyl, and lower alkoxy;
Z is selected from the group conslsting of hydrogen and chloro;
Rl is selected from the group consisting o~ hyd~ogen; alkyl and allyl;
R2 ls selected from the group consisting of alkyl, allyl7 ben~yl, hydroxyalkyl, alkynylj N alkyl amido, alkoxyalkyl, dialkoxyalkyl, alkoxy~ cyano alkyl, substituted phenyl wherein the substituent is selected from the group tri-fluoromethyl, dichloro and 3,3-dimethylureido; and Rl and R2 taken together with the nitrogen is selected from the group consisting of alkyl substituted oxazolidyl and alkyl substituted ~hiazolidyl, morpholinyl, piperidinyl and pyrrolidinyl; and salts thereof More particularly, with re~erence to the general formula above: A, B and M are as defined and X is selected from the group consisting of trifluoromethyl, lower alkyl having 1 to 3 carbon atoms, inclusive, nitro, chloro, bromog fluoroj cyano, lower alkoxy having 1 ~o 3 carbon atoms, inclusive, acetyl, lower alkylthio having 1 to 3 carbon atoms, inclusive, trifluoromethylthio and 3,3-diloweralkyl ureido in which each lower alkyl has from 1 to 2 carbon atoms, inclusive;
Y is selected ~rom the group consisting of hydrogen, lower alkyl having 1 to 3 carbon a~oms, inclusive, chloro, 1uoro, nitro, trifluoromethyl and lower alkoxy having 1 to 3 ca~bon ato~s, inclusive;
Z is selected from the group consis~ing of hydrogen and chloro;
Rl is selected from the group consistLng of hydrogen, alkyl having 1 to 6 carbcn atoms, inclus~ve, and allyl;
~2 is selected from the group consisting of alkyl having 1 to 6 carbon atoms, inclusive, allyl, benzyl, hydroxy-ethyl, alkynyl having 3 to 4 carbon atoms, inclusive, N-alk~lamido in which the alkyl has 1 to 3 carbon atoms, inclusive~ alkoxyalkyl having 2 to 6 carb~n atoms, in-clusive, dialkoxyalkyl having 3 to 6 carbon atoms, inclusive, alkoxy having 1 to 4 carbon atoms, inclusive, cyanoalkyl having 2 ~o 4 carbon atoms, inclusive, substitu~ed phenyl wherein said substituent is selected from the group trifluoromethyl, dichloro and 3,3-dimethylureidoy and Rl and R2 taken together with the nitrogen is selected fr~m the group consisting of alkyl substituted oxazolidyl and alkyl substituted thiazolidyl wherein said oxazolidyl ~L~!39(~75 or thiazolidyl is substituted 1, 2 or 3 times wi~h alkyl having from 1 to 3 carbon atoms, inclusive~ morpholinyl, piperidinyl and pyrrolidinyl; and salts thereof with an acid selected from the group consist-ing of HCl, HBr, HI, HF, H2S04, CC13COOH, 2,4-dichlQro-phenoxy ace~ic acid, 3-amino-2,5 dichlorobenzoic acid, hexanoic acid, stearic acid, naphthalene acetic acid, piYalic acid, succinic acid, 10-undecenoic acid, benzoic acid, maleic acid and malonic acid.
The terms "lower alkyl" and "alkyll' includes straight chain and branched chain substituents of this type; the term "lower alkoxy" includes straight chain and branched chain substituents of this type; the term "alkynyl" includes substituent~ of this type having straight or branched chain and at least one triple bond;
the terms "alkoxy alkyl" and "dialkyloxy alkyl" include substituents o this type ha~ing a straight or branched chain configuration; and cyanoalkyl includes substituents having at least one cyano group (CN) and alkyl ln straight or branched chain.
The compounds of this invention have been ~ound to be ac~ive herbicides; that is, the compounds ha~e been found to be herbicidally active against various species of weeds. In the broadest sense, the term "weeds" refers to plants which grow in locations in which they are not desired. As will be seen from the data which follows, these compounds show various activi~ies as pre-emergence and/or post-emergence herbicides. In some cases they have been found to show particular activity against certain weed species.
This in~ention, therefore, also relates to a method of controlling undesirable vegetation comprising applying to such vegetation or the locus where sueh vegetation is found, a herbicidall~ effective amount of a compound as described herein, and also relates ~o he~bi cldal compositions of matter comprising a herbicidally effec~ive amount of a compound as described herein plus an inert diluent or carrier suitable ror use with herbicides~
As used herein, the term "herbicide" means a compound which contro~s or modifies the growth of plants~
par~icularly of undesirable plants. By the term 'Iherbicidally effective amount" is meant an amount o~ a compound which causes a controlling or modifying effect on the growth of treated plants. The t:erm "plants" is meant to include germinant seeds, emerging seedling~ and established vegetation including roots and the above.ground -portions. Such modifying and controlling effects include all deviations from natural development, for example, killing, retardation, defoliation, desiccation, regulation~
stunting, tillering, stimulation, dwaring and the :Like.
In general, the compounds of the present .Lnven-tion can be prepared by the following methods:
I. An appropriate substitu~ed aniline (1) is reacted with an acyl chloride (2) to produce the corresponding substituted anilide ~3). The anilide is chlorinated with phosphorus chloride to prepare the sub-stituted phenyl containing imidoyl chloride (4). A
subsequent reaction with a secondary amine (4a) produces a substituted ace~amidine (5) of th~ present invention.
This sequence of reactions is depicted by the following equations:
I

~ NH2 + ClC-CM-A

(3) y 0 X~NH-C-G~-A ~ PC15 ~ 9~

z Cl R_ \ CM-A ~ R2 B
\ /

(5) Y ~ ~ N

wherein A, B~ M, Rl~ R2, X~ Y and z have the same signi-ficance as previously defined.
Reaction Scheme I
II. An alternative reaction scheme is ~he reaction of an acylchloride (6) with a primary amine (7) to produce the corresponding amide (8). This reaction is followed by treatment of the amide (8) with phosphorus pentachloride in phosphorus oxychloride as a sol~ent to produce the imidoyl chloride (9). The imidoyl chloride is reacted with a substi~uted aniline to produce the substi-tuted acetamidine (lla) or (llb) of the present invention.
This sequence of reactions is depicted by the following equations:
II
(6) ClC-CM-A ~ H N / 1 R2 B
~ 1 ~1 / Rl or R2 (8~ A-CMCN
B ¦ ~ PC15(POC13 sol~ent) ~39075 g z (9) A-CM-C ~ ~ NH2 ~ (10) B I NRl 2 ~ 2 ~Y

A-CM-C (lla) B ~NRl or R2 .HCl or z A-CM-C ~ (llb) B ~ N-H
Rl or R2 wherein Ag B, M7 Rl, R2, X, Y and Z have the same signifi-cance as previously defined Reaction Scheme II
In reaction schemes I and II, some of the individual reac~ions are performed in the presence of an organic solvent, such as acetone, methylene chloride and the like, where good chemical practice dictates. The reaction temperatures can vary from -20C to 150C. In many instances the reaction was exothermic. The reaction pressure may be atmospheric, subatmospheric or superatmospheric.
However, for convenience of conducting the reactions, ~he pressure is generally atmospheric. The reaction time will, of course, vary depending upon the reactants and reaction temperature. Generally, the reaction time is from 0.25 to 24 hours, depending upon ~he steps and rate of reaction.
After the reaction is co~ple~e, the product is recovered by separation ~rom the by-products and the solvent removed as by evaporation, or distillation. The structure is ~L~8g~5 confirmed by nuclear magnetic resonance or infrared spectra The following are representative illustrative examples for the preparation of the compounds o~ the present invention and requisite intermediates therefor. Following the examples isa table of compounds which are prepared according to the described procedures.
EXAMPLE A
Intermediate Preparation:
3' 5'-Dichloro-dichloroacetanilide .
81 grams (0.5 mole) 3,5-dichloroaniline was dissolved in a flask containing 250 milliliters of reagent grade acetone. The solution was cooled to 0C and 74 grams (0.5 mole) dichloroacetyl chloride was added dropwise with vigorous stirring with the rate of addition adjusted to maintain the reaction temperature below 5C.
When the addition was complete, 51 grams (0.50 mole) of triethylamine was immediately added dropwise with vigorous stirring, the addition rate adjusted to maintain the reaction temperature below 5C. The reaction mixture was then allowed to attain ambien~ temperature and stirred at that temperature for one hour. The mixture was poured into water, the solid product filtered off and dried giving 126 grams (92.3% yield) o~ the desired product, a white solid, m.p. 133-135C.
EXAMPLE B
ntermediate Preparation:
3',5'-Dichlorophenyldichloroacetimidoyl chloride 121 grams (0.44 mole) 3',5'-dichloro-dichloro-acetanilide and 100 milliliters of phosphorous oxychloride were combined. Phosphorous pentachloride, 92.5 grams (0.44 mole), was added and the mixture was stirred virorously with heating at reflux until hydrogen chloride evolution ceased. The phosphorous oxychloride was stripped off at reduced pressure. Distillation gave 109 8 grams (85% yield) g~5 o~ 3',5'-dichlorophenyldichloroacetimidoyl chloride con-taining a small amount of solid. The b.p. was 122-126~/0.03 millimeters.
EX~MPLE lA
N-3' 5'-Dichlorophenyl-N'-isopropyldichloroacetamidine 10.2 grams (0.035 mole) 3',5'-clichlorophenyldi-chloroacetimidoyl chloride was dissolved in a flask containing 25 milliliters of methylene chloride and the solution cooled in an ice bath. 4.5 grams (0.076 mole) isopropyl amine was added dropwise while stirring vigorously and temperature maintained below 15C. The reaction mixture was stirred at ambient temperature one hour, and washed with 100 milliliters water. The organic layer was separated~
dried over magnesium sulfa~e and stripped at reduced pressure to yield 10.7 grams (97.3% yield) of N-31,5'-dichlorophenyl-N'-isopropyldichloroacetamidine, nD30 1.5653.
EXAMPLE C
Intermediate Preparation:
N-Isopropyldichloroacetamide Dichloroacetyl chlori~e, 442.5 grams (3.0 mole), was dissol~ed in a flask containing 900 milliliters of methylene chloride and the solution cooled to 0C in an ice/acetone bath. 354 grams (5.98 mole) of isopropyl amine was added dropwise with vigorous stirring and the addition rate was adjusted to maintaln the reaction temperature below 5C. When the addition was complete, the mixture was allowed to stir at ambient temperature for one hour then washed with

2 X 500 milliliters water, the organic phase separated, dried over magnesium sulfate and stripped of solven~ at reduced pressure giving 499 grams (9~% yield) of ~he desired product, a white sol~d, m.p. 45-4&C.

EXAMPLE D
Intermediate Preparation:
N-Isopropyldichloroacetimidoyl chloride N-isopropyldichloroacetamide, 249.5 grams (2.94 mole), and 210 milliliters of phosphorous penta-chloride, 306.5 grams ~2.94 mole~, was added and the mixture was stirred vigorously and heated at reflux until hydrogen chloride evolution ceased. The phosphorous oxychloride was stripped off at reduced pressure. Dis-tillation at 4.5 millimeters gave 360 grams (65% yield) of N-isopropyldichloroacetimidoyl chloride, b.p. 63~72C.
EXAMPLE lB
-Preparation via N-isopropyldichloroacetimidoyl chlori~i N-3',5'-Dichlorophenyl-N'-isopropyldichloroacetamidine 10.5 grams (0.065 mole) of 3,5-dichloroaniline was combined with 14.7 grams (0.078 mole) of N-isopropyl 1~ dichloroacetimidoyl chloride in a flask and heated to 30C.
The reaction proceeded to 48C and was heated again until it showed an exo~herm. External heating was stopped and the reaction allowed to continue until it reached a peak exotherm of 150C and then allowed to cool to ambient temperature.
While this reaction cooled, a second reaction using the same amounts and reagents was performed. This reaction was externally heated to 50C when it began to exotherm. A peak temperature of 140C was reached while the reaction flask was in an ice water bath. Both reaction mixtures were slurried in acetone, combined and diluted with ether and the solid hydrochloride iltered off. This yielded 42.2 grams (92.7% yield) of solid m.p. 201-202C. The entire amount was treated with 200 milliliters of 10% sodium hydroxide, extracted with 2 X 250 milliliters methylene chloride~ the organic layer dried over magnesium sulfate and stripped of solvent under reduced pressure to give 36.5 gra~s (89% total yield) of an oil, nD30 of 1.5672.

7~

~YAMPLE 2 N-3'~5'-Dimethylphenyl-N'-isopropyldichloroacetamidine

3,5-dimethyl aniline, 8.9 grams (0.073 mole), and N-isopropyl dichloroacetimidoyl chloride, 15.8 grams (0.084 mole), were combined in a flask an.d the temperature immediately rose to 35C. An ice bath was applied, and when the temperature reached 45C, acetone was added to the bath. The exotherm cease~ a~ 115C, the ice bath was removed and the flask h~ated to 120C and maintained at that temperature until the mixture seemed homogeneous. A second reaction was run in the same manner, both were allowed to cool, slurried in ether, combined and filtered off as the solid hydrochloride m.p. 201-203C. The hydrochloride was then treated with 10% sodium hydroxide, extracted with methylene chloride and the organic phase dried over magnesium sulfate and the solvent stripped off at reduced pressure to give 33.1 grams (82 8% yield) o~ the desired produce with an nD30 1.5382 N-2,3-Dichlorop_enyl-N'-isopropyldichloroacetamidine 9.7 grams ~0.06 mote~ of 2,3-dichloroaniline was combined with 13.6 grams (0.072 mole) N-iso~ropyldichloro-acetimidoyl chloride and heated until the mixture started to exotherm. An ice bath was used to control, but not stop, the exothenm. After the exotherm peaked, the flask and its contents were allowed to cool to a~bient temperature and combined with a second reaction which was run in ~he same manner. These combined reactions were slurried in acetone, diluted with ether and the solid hydrochloride filtered off.
The solid was then treated with 10% sodium hydroxide, extracted with methylene chloride, separated and the organic phase dried over magnesium sulfate. The solvent was then stripped off at reduced pressu~e to give 31.1 grams (82.7%
yield) of the desired produce, an oil, nD30 1.5668.

s EXiMPLE 4 N-3-Chloro-2-methyl~henyl-N'-isopro~yldichlor~acetamidine 3-chloro-2-methylaniLine 9 10 grams (0.035 mole~, and N-isopropyldichloroacetimidoyl chloride, 7.9 grams (0.042 mole), were combined in a flask, heated to initiate the reaction and the rate of exotherm controlled, but not stopped, with the application of an ice bath. After the exotherm subsided, the reaction flask was allowed to cool to ambient temperature and the contents slurried with acetone diluted with ether. The solid product was filtered off giv-ing 10.0 grams (97.7% yield) of ~he hydrochloride which decomposed at 236C. 5 grams (0.015 mole) of this hydro-chloride was treated with 10% sodium hydroxide to give 4.3 grams (0.014 mole) of an oil, nD30 1.5440.
E~AMPLE 5 N-m-Trifluoromethylphenyl-N'-allyldichloroacetamidine Allyl amine, 3 grams (0.053 mole), was dissolved in a flask con~aining 25 millili~ers o~ methylene chloride Meta-trifluoromethylphenyl dichloroacetimidoyl chloride, 7.6 grams (0.026 mole), was added dropwise while s~irring and maintaining ambient temperature with a water bath. The mixture was allowed to stir one houre, washed with water, the organic phase separated and dried over magnesium sulfate and the solvent stripped at~reduced pressure to give 6.9 grams ~85 2% yield) of an oil, nD30 1.4986.

N-m-Trif~uoromethylphenyl-N',N'-tetramethylenedichloro--acetamidine . .
Pyrrolidine, 3.6 grams (0.051 mole)~ was combined in a flask with 25 milliliters of methylene chloride. Meta-trifluoromethylphenyl dichloroacetlmidoyl chloride, 7.3 grams (0.025 mole), was added dropwise while stirring and maintain-ing ambient temperature with a water bath. The mixture was allowed to stir one hour at ambient temperature, washed with 7~S

water, the organic layer dried over magnesium sulfate and stripped of solvent to give 8.0 grams (98.8% yield) of an oil, nD30 1.51~0.
EX~MæLE 7

4-(N-m-Trifluoromethylphenyl dichloroacetimidoyl~ morpholine Morpholine, 4.2 grams (0.0482 mole), was combined in a flask with 25 milliliters of methylene chloride. Meta-trifluoromethylphenyl dichloroacetim-doyl chloride, 7 grams ~0.024 mole), was added dropwise while stirring and main-taining ambient temperature with a water bath. The mixture was allowed to stir at ambient temperature one hour 3 then washed with water, the organic phase separated, dried over magnesium sulfate and the solvent stripped off at reduced pressure ~o give 7.3 grams (89% yield) of an oil, D30 1.5184.

3~N-m-TrifluoromethvlDhenvl dichloroace~imidoYl 2,2 S-tri methyl oxazolidine Twenty-two milliliters (0.048 mole) of a solution of 2,2,5-trimethyl oxazolidine in benzene (4 milliliters =
1 gram in benzene) was combined in a flask with 15 milli-liters o~ methylene chloride. Meta-trifluoromethylphenyl dichloroacetimidoyl chloride, 6.7 grams (0.023 mole), was added dropwise while stirring and maintaining ambient temperature with a water bath. The mixture was allowed to stir at ambient temperature one hour~ washed with water, the organic layer separated, dried over magnesium sulfate and stripped of solvent to give 6.5 grams (76.5% yield) of an oil, nD30 1.4818.
EXAM_ 9 Preparation of Intermediate.
N-Iso ro 1 chlorofluoroacetamide P PY
A solution of 11.8 grams (0.2 mole) isopropyl amine in 20 milliliters ethyl a~cohol were added dropwise a~

1~9(~

10-15C with stirring to a solution of ethyl fluorochloro-acetate and 5 drops of ethylene glycol in 80 milliliters ethyl alcohol. The solution was stirred at 10-20C for 2 hours and was then stored at -15C for 3 days. At this time, the solution was evaporated to leave a liquid, 25.2 grams, nD30 1.43g5, identified as the title compound by infrared and nuclear magnetic resonance spectroscopy~
Preparation of Intermediate:
N-Isopropyl chlorofluoroacetamide In a 100 milliliter flask were placed 22 grams (0.14 mole~ of N-isopropyl chlorofluoroacetamide and 3 milliliters of phosphorous oxychloride. Pulverized phos-phorous pentachloride9 30.0 grams (0.14 mole), was added to this mixture at an initial temperature of 32C. The temperature rose to 42C over the course of the addition.
After all the phosphorous pentachloride had been added, the mixture was heated. The majority of the hydrogen chloride was evolved at 40C and by the time the temperature reached re~lux (120C), gas evolution had ceased. The mixture was next distilled at atmospheric pressure using a 15 centimeter glass - helix packed column with attached variable takeoff condenser to give 17.8 grams of product, b.p 136-138C, identified as the title compound by infrared and nuclear magnetic resonance spectroscopy.
N-(3 2 5-Dimethylphenyl)-N'-isopropyl chlorofluoroacetamidine In a 100 milliliter flask was placed 5.0 grams (0.03 mole) of N-isopropylchlorofluoroacetimidoyl chloride.
A thermometer and air-cooled condenser were attached to the flask. To this was added 2.8 grams (0.02 mole) of 3,5-dimethylaniline. There was an immediate increase in tem-perature and formation of a whi~e solid. I~hen the temperature reached 70C, a cold bath was applied to moderate the reaction and when no further isotherm was observed, t~e mixture was heated to 140C with a heat-gun.
The mixture was then allowed to return to room 1~890~5 temperature and the resulting dark oil was taken up in acetone, addition of pentane caused a solid tQ separate which was removed by filtration. This solid was mixed with 50 milliliters methylene chloride and shaken with 50 milliliters of 10~/~ sodium hydroxide. The organic layer was separated, washed twice with 50 milliliters portion of water and dried over magnesium sulfate.
Removal of solvent in vacuum lef~ an oil, 3.6 grams, nD30 1.5229, which was identified by infrared and nuclear ma~netic resonance spectroscopy to be the title compound. The oil eventually crystallized to a solid of m p. 37-40C.
~XAMPLE 10 N-C~3-Dichlorophenyl)-N'-isopropyl chlorofluoroacetamidin_ The above procedure was repeated with 5.0 grams (0.03 mole) N-isopropylchlorofluoroacetimidoyL chloride and 3.7 grams (0.02 mole) of 2,3-dichloroaniline to yield 3.7 grams of a dark oil, identified by infrared and nuclear magnetic resonance spectroscopy to be the title compound.
~XA~LE 11 N-(3~5-Dichlorophenyl)-NI-isoprop2~ chlorofluoroacetamidine The above procedure was repeated with 5.0 grams (0.03 mole) N-isopropylchlorofluoroacetimidoyl chloride and 3.7 grams (0.02 mole~ of 3,5-dichloroaniline to yield 4.9 grams of an oil, nD3 1.55409 identified by infrared and nuclear magnetic resonance spectroscopy as the title com-pound.

Preparation of Intermediate:
N I30FIropylbr~mofluoro acetamide A solution of 14.8 grams ~0.25 mole) isopropyl amine in 25 milliliters ethanol was added dropwise to a solution of ethyl bromofluoroacetate, 40 grams (0.22 mole), and 5 drops ethylene glycol in 100 milliliters ethyl alcohol at 10-15C. The solution was stirred at 10-20C for 2 hours and was then stored at -15~C for 3 days. At this time, the solution was evaporated to leave a liquid, 41.8 grams, nD30 1.4629, identified by infrared spectroscopy as the title compound.
Preparation of Intermediate:
N-Isopr pylbromo1uoroacetimidoyl bromide -In a lO0 milliliter flask fitted with a gas-inlet, 10 thermometer, magnetic stirrer and reflux condenser were placed 20.0 grams (0.1 mole) of N-isopropylbromofluoro-acetimidoyl bromide Argon was flushed through the system and after 15 minutes, 27.3 grams (0.1 mole) of phosphorous tribromide were added in one portion. The temperature rose 15 to Q8C. Cooling was applied with an ice bath and bromide, 1.1 grams (0.1 mole) was added slowly with stirring. ~ter addition was complete, the mixture was allowed ~o come to room temperature and after one hour it was heated to 85-90C.
The argon purge was maintained throughout the heating period.
20 After 1 1/2 hours the evolution of HBr had ceased and the mixture was cooled to lO~C and filtered free oX phosphorous oxybromide. The filtrate was vacuum distilled to yield 16.4 grams, b.p. 53-60C at 1 millimeter. Identified by infrared spectroscopy as the title compound.
25 N-(3,5-Dichlorophenyl)-N'-isopropyl bromofluoroacetamidine In a 100 milliliter ~lask was pLaced 5.0 grams (0.02 mole) of the above lmidoyl bromide. A thermometer and air cooled condenser were attached to the flask. To this was added 3.1 grams ~0.02 mole) of 3,5-dichloroaniline. The 30 temperature rose slowly to 70C, and at 70C an ice bath was used to moderate the reaction. ~en no further exotherm was observed, ~he mixture was heated to 135~C and was then al-- lowed ~o cool. The residue was taken ~p in 50 milliliters methylene chloride and this solution was carefully shaken 35 with 50 milliliters of 10% sodium hydroxide solution. ThP

9~

organic layer was then shaken wi~h 50 milliliters of a saturated salt solution and dried. Removal of solvent in vacuum left an oil, 2.9 grams, identified by infrared and nuclear magnetic ~esonance spec~roscopy as the title compound.

Preparation of Intermediate:
N-Isopropyldifluoroacetamide A solution of 20 grams (0.16 mole) of ethyl difluoroacetate in 20 milliliters ethyl alcohol was added slowly in a solution of 9.5 grams (0.16 mole) isopropyl-amine and 5 drops of ethylene glycol in 30 milliLiters ethyl alcohol. The temperature rose slowly to 27C. The mixture was then refluxed for 3 days. After this reflux period, the solution was evaporated at 100 millimeters and the residue was distilled at atmospheric pressure to yield 18.0 grams, b.p. 86-88, identified by infrared spectroscopy as the title compound N-Isopropyldifluoroacetimidoyl bromide In a 100 milliliter flask fitted with thermometer, gas-inlet, and magne~ic s~irrer was placed 12.0 grams (0.09 mole) of N-isopropyldifluoroacetamide. Argon was flushed through the system and phosphorous tribromide, 27.3 grams ~0.09 mole), was added slowly at 10-15C. Bromine, 14.0 grams (0.09 mole)~ was then added slowly at 10-15C with ~5 s~irring. After all the bromine was added~ the mixture was allowed to come to room temperature and was then heated with argon sweep at 85-90C Heating was continued ~or 2 hours.
The mixture was next cooled to 0C and filtered free of phosphorous oxybromide. The ~iltrate was vacuum distilled to yield 4.0 grams, b.p. 34 38 (50 millimeters identi-fied by infrared spectroscopy as ~he title compound.

N-(3,5-DichloroPhenyl)-N-isopropyldifluoroacetamidine A solution of 3.2 grams (0.02 mole~ of 3,5-dichloroaniline in 50 milliliters toluene was heated to reflux (111C) and 4.0 grams (0.02 mile) of N-isopropyldi-fluoroacet~nidoyl bromide was added slowly. A vigorous reaction occurred with separa~ion of solid. The mixture was refluxed for 1/2 hour after addition was complete, cooled and filtered to give 6.0 grams of the hydrobromide sal~. The solid was slurried in 50 milliliters methylene chloride in a separatory funnel and this mixture was shaken with cold 5% sodium hydroxide solution. The mixture was phase-separated and washed with two 50 milliliter portions o~ water. Evaporation of solvent after drying leEt 3.9 gr~ms of a liquid, nD30 1.5425, identified by infrared and nuclear magnetic resonance spectroscopy as the title com-pound.
Dichloroacetamidine Salt Examples Trifluoroacetic Acid Salt of N-(3,5-Dichlorophenyl)-N'-isopropyl dichloroacetamidine The amidine (3.1 grams~ 0.01 mole) and the trifluoroacetic acid (1.1 grams, 0.01 mole) were combined in 35 millili~ers ethyl ether and the mixture allowed to stir ov~rnight at room temperature, refluxed for 45 minut2s and the solvent removed in ~acto. The product was a very viscous semi-solid. Yield: 2.0 grams (47.6%). Infrared indicated the product was the expected salt.

Composition of Pivalic Acid and N-~3,5-Dichlorophenyl-N'-isopropyl dichloroacetamidine The amidine (3.1 grams, 0.01 mole) and pivalic acid (1.0 grams, 0.01 mole) were combined in 35 milliliters tetrahydrofuran. The mixture was stirred 1/2 hour at room -21^
temperature and refluxed 2 hours. The solvent was removed giving a tan oil, nD3 1.5192. Yield: 4.0 grams (97.5%).
Infrared indicated a composition of pivalic acid and amidine.

Com~osition Df 10-Undecenoic Acid and N-(3 ? 5-Dichloropheny~
N'-iso ro 1 dichloroacetamidine P PY
Sa~e procedure as in Example 15. There was ob~ained a tan oil, nD30 1.5163. Yield: 4.5 grams ~91.8%).
Infrared confirmed the expected title composition.
EX~MPT ,F_1 7 Composition of Succinic Acid and N-(3,5-Dichlorophenyl)-N1-iso ro vl dichloroacetamidine P P, _ _ Same procedure as in Example 15 using the acet-a midine (3.1 grams, 0.01 mole) and succinic acid (0.6 grams, O.OOS mole). Viscous semi-soLid. Yield: 2.1 grams (56.8%). Infrared confirmed the expected title composltion.
The following is a table of compounds which are prepared according to the aorementioned procedures. Com-pound numbers have been assigned to them and are used for identification throughout the balance of the specification.

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11 i~3~iO~5 HE~BICIDE SCREENING TESTS
As previously mentioned, the herein described compounds produced in the above-described manner are phytotoxic compounds which are useful and valuable in con-trolling v~rious plant species. Compounds of this inven~ion were tested as herbicides in the following manner.
A._ Pre-emergence Herbicide Screening Test Using an analytical balance, 300 mill~grams of the compound to be tested is weighed on a piece of glassine weighing paper. The paper and compound are placed in a 2 oz. amber bottle and dissolve in 45 milliliters o~ acetone.
If the material is not soluble in acetone, another solvent such as water, alcohol, or dimethylformamide (DMF) is used.
When DMF is used, only 1.5 milliliters o less are used to dissolve the compound and then another solvent is used to bring the volume to 45 milliliters. Twenty millill~ers o this solution ~g transferred to a 80 m~llillter wide~mouth amber bottle and diluted with 24.5 milliliters o~ a water and acetone mixture (lO:l) containing 1% Tween 20 ~ (polyoxy-ethylene sorbitan monolaurate). The solution is sprayed on the seeded flat on a linear spray table calibrated to deliver 80 gallon per acre, the application rate is 2 lb/acre ~2.24 kg/hectare).
When applied at 8 lb/acre (8 . 96 kg/hectare), 20 milligrams of the compound to be tested are weighed onto a glassine weighing paper, placed into a 30 milliliter ~ial, and dissolved in 3 milliliters acetone containing 1%
Tween 20 ~. If the material is not soluble in acetone, another solvent such as water, alcohol, or dimethylformamide (DMF~ is used. When DMF is used, only 0.5 milliliters or less are used to dissolve the compound and then another solvent is used to bri~g the volume to 3 milliliters. The solution is atomized onto the seeded fla~ using a No. 152 De~ilbiss atomizer at a pressure of 5 lb/square inch (0.35 kg/cm2), and the spray volume was 143 gallons per acre (1338 liter per hectare).

s On the day preceeding treatment, a flat is filled with sandy loam soil fortified with 50 ppm 17-17-17 erti-lizer and Captan ~. Seven rows are Lmpressed across the width of the flat and seeded with one species per row. The sePds are covered with soil so that they are planted at a depth of 1.2 centimeters. The species are hairy crabgrass ~CG) (Dig~taria san~uinalis), foxtail (FT) (Setaria spp ), watergrass (WG) ~Echinochloa crus~ali), wild oat (WO) tAvena fatua), mustard (MD) (Brassica juncea), curly dock (CD) (Rumex crispus), and pigweed (PW) (Amaranthus retro~lexus~ is seeded between the last row and the end of the flat at a depth of 1 centimeter. Ample seeds are planted to give about 20 to 50 seedlings per row after emergence depending on the size o~ the plant at the time of rating. At the 8 lb/acre testing rate red oat (RO) (~ena sativa) is used instead of wild oat.
~fter treatment, the ~lats are placed in the green-house at a temperature of 70 ~o 85F and water by sprinkling. Two weeks after treatment the degree of lnjury or control is determined by comparison with untreated plan~s of the same age. The injury rating is recorded as 0 to 100%
for each species where 0 represents no inju~y and 100%
represe~ts complete kill.
B. Post-emergence Herbicide Screening Test The procedure for this test is substantially the same as the pre-emergence herbicide screening test A. The seeds of the plant species or the 2 lb/acre test are described in screeninO test A. The seeds for ~he 8 lb/acre post-emergence test included: hairy crabgrass, watergrass, red oat, mustard, curly dock and pinto beans (BN) (Phaseolus vulgaris). The flats are seeded and placed in the greenhouse 8-12 days prior to treatment with the candidate compounds.
The plan~ foliage was sprayed with solutions v~ the candidate compounds.
For the 8 lb/acre solutionS 20 milligrams of the test compound was weighed out and dissolved as described above except that 2.5 milliliters acetone with 1%
Tween 20 ~ or other suitable solvent plus 2.5 milligrams o water was atomized as described above. The spray volume was 238 gallons per acre (2226 liters per hectare). The rate at 2 lb/acre (2.24 kg/hectare) was achieved using the linear spray table as described above.
The results of these tests are shor~n in Table II.

'75 TABLE II
Herbicida~ Activity - Screening Results Percent Control a~ 8 lb/A
. .
Compound Pre emergenc e Pos t - ernergenc e N~er CG F~G R0 PW Mi) CD CG WG R0 ~ CD BN
90 80 8(~ 0 0 0 0 0 0 () 0 0 0 90 80 $() 70 0 0 0 0 0 0 0 (3 0 3 ~ 0 0 0 0 0 0 80 70 0 100 80 40 ~, o o o o o o o o o o 100 0 0

6 80 80 80 60 100 30 20 0 0 0 0 0 0

7 40 40 0 0 0 0 0 0 100 0 0

8 0 0 0 0 0 0 0 20 0 0 0 0 10

9 0 0 0 0 30 0 20 0 0 0 0 0 0 0 0 0 0 80 0` 0 11 0 0 0 0 0 30 0 100 95 30 lO0 ~0 ~0 ~3 100 99 99 90 45 20 45 95 95 0 0 20 1~ 99 96 95 30 0 0 35 95 95 0 0 20 0 99 ~8 98 99 0 0 65 98 95 10 0 2~ 0 18 95 95 90 95 0 0 ~5 95 95 0 0 20 10 ~9 80 80 60 1~ 0 0 0 95 95 0 o 0 0 80 80 80 0 35 20 ~0 95 6~ 0 20 20 10 21 0 0 0 0 0 ~ 0 0 0 0 10 0 0 ~3 0 0 0 0 0 0 0 0 0 0 50 0 0 ~4 ~ 40 4û 0 20 10 20 95 80 0 0 30 10 ~9~)7~;

TABLE II (Cont'd) Compound Pre-emer ence Post-emergence ~umber CG FT WG Rg PW MD CD CG WG R0 MD CD BN

26 0 0 0 9~ 60 0 0 0 0 0 0 0 32 0 0 0 0 0 0 0 4~ 40 0 0 0 0 0 0 0 0 0 0 0 lO0 60 20 0 0 0 0 0 0 0 80 ~0 0 0 0 0 46 100 99 98 60 98 40 ~5 ~5 80 30 40 40 50 4g 100 9g 9~ lO 97 ~0 70 90 80 3~ 50 50 50 99 99 98 2~ 30 0 20 95 80 60 70 60 10 39~37 TABT.E II ~Cont ' d~
Compo~dPre-emer~ence Post-emer ence NumberCG F~O~I~ MD CD CG_W(~ BN

52 98 98 ~0 30 50 20 60 98 80 40 40 4050 90 30 30 0 95 0 0 0 0 ~ 0 0 0 58 1~0 98 98 0 80 20 70 95 95 30 3020 0 59 o o o o o o 0 95 80 0 0 0 g8 95 95 0 0 0 0 40 20 0 0 0~ 30 62 97 95 95 0 0 0 0 9~ 80 0 100 40 10 ~4 100 100 100 95 80 10 80 0 0 0 0 0 20 100 100 lO0 97 50 ~0 95 0 0 0 0 0 20 71 10~ 100 99 0 0 ~0 30 0 0 0 20 3030 72 100 95 go 30 0 0 0 0 0 ~ o o o 74 100 g8 98 ~0 20 0 0 90 40 20 20 0 30 100 100 100 50 99 50 80 98 9~ 20 2030 40 76 100 100 100 20 g~ 20 0 98 gO 0 0 20 10 ~ABLE II (Con~ ' d2 Cor~3o~dPre-emer ence Post-emer ence NumberCG F'l` WG R~ P~J MD CD CG ~ R0 ~CD BN
77 ~ 00 99 99 0 80 10 20 90 60 0 0 0 30 78 100 98 98 0 10 20 0 30 30 0 0 ~ 2~
79 100 100 10~ ~0 80 20 90 0 0 0 0 0 10 81 100 ~00 100 0 98 80 90 9~ 60 0 10 20 30 82 ~00 99 99 0 95 40 70 80 80 0 20 20 40 84 100 100 99 10 80 50 ~5 95 90 0 20 30 40 87 98 98 50 0 0 0 0 95 80 10 30 30 ~0 91 100 100 100 90 99 95 95 ~8 95 ~0 80 80 8~

94 100 100 99 20 90 90 98 95 98 90 9~ 9S 80 96 100 100 99 20 95 40 gO 95 80 20 40 80 40 98 1~0 99 ~9 20 97 10 60 95 60 0 10 ~ 30 99 100 98 98 20 60 30 50 g5 80 1~ ~0 80 40 100 100 100 100 80 9~ 10 80 98 8¢ ~) 0 90 40 101 100 98 99 30 g8 10 50 9~ 70 10 ~0 80 30 TABLE II (Cont ' d) Compo~mdPre - emer~;enc e Pos t - emer~;enc e NumberCG FT WG R0 P'W ~D CD CG WG R0 2~[) eD BN
103 99 98 95 60 99 3~) 70 95 70 20 10 30 40 105 99 3t3 20 10 98 0 0 0 ~) O 10 0 0 106 ~00 100 99 20 95 40 50 9~ 90 40 ~00 60 3V
107 95 90 ~0 10 0 0 0 70 ~ O 30 0 108 9~ 97 97 20 98 10 30 99 60 10 20 30 40 109 0 0 0 ~ 0 0 0 80 10 0 30 0 0 110 100 50 80 30 0 0 0 30 0 ~ 10 0 0 1~2 98 40 40 0 60 0 0 0 0 0 10 0 0 1~3 70 20 20 0 0 10 0 0 0 0 0 0 0 11~ 100 ~9 99 97 ~0 0 70 98 90 10 0 60 40 llS 100 99 99 40 30 20 80 98 95 80 0 100 40 11~ 99 98 95 0 0 0 0 98 30 20 0 0 30 119 98 98 95 30 0 0 0 ~ 10 0 0 30 ~0 120 99 97 98 30 20 0 10 ~8 80 20 0 50 40 121 100 9~ ~7 80 0 0 0 99 98 30 0 98 30 ~24 99 97 98 80 0 0 40 70 30 0 0 0 0 127 - 100 10{) 99 99 95 99 - 9~) 0 40 40 ~0 128 - 100 100 99 98 9~ 99 - 80 10 40 40 `40 -53~
TABLE II (Con~ ' d) Compo~d Pre-emer~ence Post-emer ence Number CG FT WG R0 PW MD CD CG W(~ RO ~ cb BN
129 ~ 100 100 9S 9~ 40 ~8 - ~û 0 0 0 10 131 - 9~ 98 20 80 60 70 - 0 0 0 0 10 134 100 100 9g 95 20 40 - 40 10 0 0 30 136 - 98 95 lO 0 0 0 - 0 0 0 0 0 144 - 100 ~00 100 98 98 95 - 80 0 30 0 30 145 - lO0 100 97 95 95 98 - 80 0 0 0 40 1~6 - 80 95 10 0 0 0 - 0 0 0 0 0 149 - 100 ~00-97 98 97 99 - 80 0 30 0 7Q
lS0 - 100 100 40 ~0 3~ 0 - 60 0 30 0 0 152 - .100 99 70 20 0 0 - 60 0 30 0 0 153 - 100 100 98 40 30 8û - 95 0 40 0 60 5~
TABLE II (Cont ' d~
Compo~dPre-emer~nce Post-emergence NumberCG FT WG R0 _ PW MD CD _CG WG R0 MD CD BN

159 - 4~ 50 20 0 0 0 - 0 0 0 0 0 165 -' 100 ~00 ~00 50 70 20 - 30 20 10 0 0 166 - 100 ~00 100 80 80 80 - 90 30 0 0 ~0 168 - 80 70 0 0 0 0 - O O û 0 20 169 - 100 98 30 40 0 40 - g5 0 30 ~0 50 170 - 100 99 40 50 30 50 - ~5 20 ~0 ~0 60 171 - 98i g8 98 0 0 0 - 60 0 0 0 0 175 - 9~98 30 0 0 0 - 60 10 0 0 0 176 - 9998 ~) 40 0 20 - 70 1~ 0 0 10 17~ - 98 98 30 97 0 20 - 90 30 0 0 0 179 - 9~ 70 0 0 0 0 - 60 0 0 0 0 180 - 9999 10 ~0 20 3~) - 95 0 20 ~ 0 v~

TABLE II (Cont'd~
Compound Pre emer~ence Post-emer~ence Number CG FT WG R0 PW Ml) CD_ CG li~G R0~ P~ ~ BN
181 - 30 50 20 90 100 0 - 90 98 10~ ~00 100 Percent Control at 2 lb/A
CQmpound Pre~emergence Post-emergence Number CG FT WG W0 MD CD PW CG FT WG W0 MD CD PW
183 - 80 98 80 lO 0 10 - 80 B0 20 20 0 10 1~4 - 100 100 100 10 98 90 - 99 95 70 100 98 100 185 - lO0 100 ïO0 98 g9 100 - 80 90 20 ~0 30 0 ~86 - 20 10 10 0 0 0 - 0 0 0 0 0 0 18~ -' 99 96 80 0 0 0 - 20 20 0 0 0 0 189 - 100 98 .40 0 0 0 - 50 40 0 0 0 0 190 - 0 20 0 0 0 0 - 0 ~ 0 0 0 0 193 - 100 lO0 60 0 0 0 - 30 40 0 0 0 0 194 - 20 ~0 0 0 0 0 - 0 0 0 0 0 0 195 ~ 20 60 0 0 0 0 - 0 0 0 0 0 0 196 - 0 0 0 0 0 0 - 20 0 0. 0 0 0 1~8 - 40 60 0 0 0 0 - 20 20 0 0 0 0 199 - 100 100 7~ ~0 9~ 40 - 90 90 30 4~ 40 30 200 - 0 0 0 0 0 0 - 80 60 0 lO 70 20 20~ - 0 0 0 0 0 0 - ~0 40 0 ~0 70 40 9~7~i -5~-TABLE II (Cont'd~
Compound Pre-emergence Post~emergence Number CG FT WG W0 MD CD PW CG FT WG W0 MD_ CD PW
2~3 - 100 100 98 30 9~ 0 - 90 80 20 30 50 50 204 - 100 100 90 30 80 0 - 90 80 20 30 60 ~
205 - 100 100 80 0 90 9~ - 710 ~0 20 20 30 20 ~06 - ~0 100 80 g5 98 30 - 80 80 10 30 20 100 207 - lOd 100 80 60 100 100 - 80 80 80 40 60 20 209 - ~0 0 0 50 60 90 - 0 0 40 40 60 40 21~ - 70 50 0 0 40 0 - 60 0 0 70 70 60 Percent Control at 8 lb/A
CompoundPre-emer ence Post~emergence NumberCG F~ WG Rg P~ MD CD CG WG R0 MD CD BN
213 98 99 9~ 40 0 0 40 95 9S 20 10 20 30 214 100 100 100 20 90 30 85 g5 90 0 0 20 50 215 100 lOQ 100 98 80 60 95 100 95 20 0 0 50 216 100 100 100 ~0 80 30 80 100 9~ 0 0 0 ~0 221 100 100 100 70 90 60 95 98 90 0 ~0 30 50 222 100 100 100 98 99 97 98 ~ 80 70 40 80 98 223 99 97 98 ~0 30 0 60 ~00 90 0 0 100 ~) 224 ~00 98 98 95 50 30 40 98 90 20 10 40 40 TA:BLE II ~Con~ ' d) Compound Pr~emer~enpl/~ ~ CD P st-~ e 225 100 99 ~5 60 30 0 40 98 95 20 10 40 40 227 g8 98 30 0 0 0 0 80 20 0 0 0 228 98 98 95 20 0 0 0 9~ 30 0 0 ~ 30 2~9 9g 98 98 98 ~ 0 0 99 90 30 0 50 30 230 ~8 80 80 80 0 0 0 98 90 10 0 100 40 231 0 0 o o o o o go o o o o o 239 - 95 98 20 80 60 70 - O û 0 0 10 241 - 80 g5 0 0 0 0 - 0 0 0 0 10 244 - 40 4~ 0 0 0 0 - 0 0 0 0 0 245 - 95 95~ 10 0 0 ~ - 0 0 0 0 0 246 - 90 98 20 60 0 0 - 60 ~ 0 30 248 - 30 0 0 0 0 0 - o o o o o 249 - 9~ 98 40 0 0 0 - ~0 0 0 0 10 250 - 99 ~00 0 30 40 ~0 - 60 0 0 0 0 TABLE II ~Con~ ' d) Compound ~re-emer~ence ~
Number_ CG FT WG R0 PW MD CD CG WG R0_MD CD BN

253 -100 100 10~ 98 98 98 - 70 0 30 0 40 2~8 -100 100 30 0 0 0 - 40 0 0 0 0 263 -.100 100 70 90 90 95 - 30 0 0 0 20 2~4 -0 40 10 0 0 0 - ~ 0 0 0 0 2 65 -98 98 97 0 ~ 0 - 0 0 0 0 0 267 -lO0 100 90 60 80 95 - 80 0 S0 0 60 ~69 -80 90 10 30 0 ~0 - 0 0 0 0 0 270 -0 70 0 0 0 0 - 0 o 0 0 0 274 - 95 90 80 50 70 20 - O û 0 0 O
275 - 109 ~00 lO0 80 80 80 - 80 20 10 1~ 0 276 - ~0 0 0 0 0 0 _ o 0 0 0 0 TABLE II (Cont'd) Compo~d Pre-emergence Post-emer~ence Number CG FT WG _ R0 PW MD CD CG WG R0 MD_ CD_ BN
__ ~77 - 99 g8 10 40 0 40 - 80 20 10 lû 30 280 - 60 g5 20 0 0 0 - 0 0 0 0 0 2~3 - 100 100 100 100 100 100 - 90 60 100 90 100 Percent Control at 2 lbJA
Compound Pre-emerg~ CD PW Post-emer~ence 285 - 100 ~00 30 10 90 60 - 90 90 40 40 40 0 286 - 100 40 10 80 80 20 - 40 ~0 20 80 70 0 287 - lOû 100 95 95 100 100 - 9~ 70 60 75 70 100 ~90 - 100 100 98 98 ~00 100 - 65 70 50 40 ~0 30 2~1 - lO0 100 ~OQ 95 100 lO0 - 75 75 60 30 60 0 292 - 100 100 ~00 95 100 100 - 70 75 60 60 70 50 293 - ~00 100 100 98 100 100 - 80 75 60 60 60 30 294 - 100 100 95 ~0 100 100 - 70 75 75 60 60 100 For practical use as herbicides the compounds of this invention are generally incorporated into herbicidal compositions which comprise an iner~ carrier and a herbici-dally toxic amoun~ of such a compo~nd. Such herbicidal compositions, which can also be called ormulations, enable the ac~ive compound ~o be applied conveniently to the site of the weed infestation in any desired q~ntity.
Useful ormula~ions of the compounds of the pre-sent invention can be prepared in conventional ways. They include dusts, granules, pelletsg solutions, suspe~sions, emulsions, we~able powders~ emulsifiable concen~rates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used at spray volume of from a few liters to several hundred liters per hectare. High streng~h compositi~ns are primarily used as intermediates for further ormulation. The ormula~ions, broadly, contain about 1% to 99% by weight of ac~ive ingredient(s~ and at least one o (a) about 0.1% to 20%
surfactant(s) and (b~ about 5% to 99% solid or liquid diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:
Percent by Wei~ht c~ive In~redient Diluent~s~ Surfactant(s) Wettable Powders 20-90 0-74 1-10 Oil Suspensions, Emulsions, Solutions (including Emulsifi-able Concentrates) 5-50 40-95 0-15 Aqueous Suspensions10-50 40-84 1-20 Dusts 1-25 70-99 0-5 Granules and Psllets1-95 5-99 0-15 High Strength Compositions 90-99 0-10 0-2 Lower or high levels o active ingredient can, of course, be presen~ depending on the intended use and the p~ysical properties o~ the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank m~xing.

75i Compositions including ac~ive compounds alss may be applied by addition to irrigation waters supplied to the field to be treated. This method of application permits pene~ration of the compounds into the soil as the water is absorbed therein. Compositions applied to the surface of the soil can be incorporated and distribllted below ~he surface of the soil b~ conventional means such as discing or mixing operations.
The compositions can also comprise such additional substances as other pesticides, such as insecticides, nematocides9 fungicides, and ~he like; stabilizers, spreaders, deactivators, adhesives, stickers, fertilizers, activators, synergists, antidotes, and the like.
The compounds of the present invention are also useful when combined with other herbicides and/or defoliants, dessicants, growth inhibitors, and the like in the herbicidal compositions heretofore described. These other materials can comprise from about 5~/O to about 95~/O o the active ingredients in the herbicidal compositions. Use of combinations o these other herbicides and/or defoliants, dessicants, etc. with the compounds of the present invention provide herbicidal compositions which are more effective in controlling weeds and often pro~ide results unattainable wi~h separate composi-tions of the individual herbicides.
The other herbicides, defoliants, dessican~s and plant growth inhibi~ors, with which the compounds of this invention can be used in the herbicidal eompositions to control weeds, can include chlorophenoxy herbicides such as 2,4-D, 2,4,5-T, MCPA, MCPB, 4~2,4-DB), 2,4-DEB, 4-CPB, 4-CPA, 4-CPP, ~,4,5-TB, 2,4,~-TES, 3,4-DA, silvex and the like; carbamate herbicides such as IPC, CIPC~ swep, barban, BCPC, CEPC, CPPC, and the like; thiocarbamate and dithio-carbamate herbicides such as CDEC, metham sodium, EPTC3 diallate, PEBC, perbulate, vernolate and the like; substi-tuted urea herbicides such as nore sifuron, dichloral urea3 chloroxuron~ cycluron, fenuron, monuron, monuron TCA, diuron, linuron, monolinuron neburon, buturon, trimethuron and the like; symmetrical triazine herbicides such as simazine, chlorazine, atraone, desmetryneg norazine3 ipazine3 prometryn, atazine, ~rietazine, simetone, prome-tone, propazine, ametryne and the like; chloroacetamide herbicides such as 4-(chloroacetyl)morpholine, l-(chloroacetyl)-piperidine and the like; chlorinated aliphatic acid herbicides such as TCA, dalapon, 2,3-di-chloropropionic acid, 2~2g3-TPA and the like; chlorinated benzoic acid and phenylacetic acid herbicides such as 2,3,6-TBA, 2,3,5,6-TBA, dicamba, tricamb~, amiben, fenac, PBA, 2-methoxy-3,6-dichlorophenylacetic acid, 3-methoxy-2,6-dlch1Orophenylacetic acid, 2-methoxy-3,5,6-trichloro-phenylace~ic acid, 2,4-dichloro-3-nitrobenzoic acid and the like; and such compounds as aminotriazole, maleic hydrazide, phenyl mercuric acetate, endothal, biuret, technical chlordane, dimethyl 2,3,5,6-tetrachloroterephthalate, diquat~ erbon, DNC, DNBP, dichlobenil, DPA, diphenamide, dipropalin, trifluralin, solan, dicryl, merphos, DMPA, DSMA, MS~A, pottasium azide, acrolein, benefin, bensulide, AMS, bromacil, 2-(3,4-dichlorophenyl)-4-methyl-1,2,4-oxazolidine-3,5-dione, bromoxynil, cacodylic acid, CMA, CPMF, cypromid, DCB, DCPA, dichlone, diphenatril, DMTT~ DNAP, EBEP, EXD, HGA, ioxynil, IPX, isocil, potassium cyanate, MAA, MAMA~
MCPES, MCPP, MH, molinate, NPA, OCH, paraquat, PCP, picloram, DPA, PCA, pyrichlor, sesone, terbacil, terbutol, TCBA, brominil, CP-50144, H-176-1, H-732, M-Z901, planavin, sodium tetraborate, calcium cyanamid, DEF, e~hyl xanthogen disul-fide, sindone, sindone ~, propanil and the like.
Such herbicides can also be used in the methods and compositions of this invention in the form o their salts, esters, amides, and other derivatives whenever applicable to the particular parent compounds.
Weeds are undesirable plants growing where they are not wanted, having no relative economic value, and interfering wi~h the produc~ion of cul~ivated crops, with the growing of ornamental plants, or with the welfare of li~estock.

Similarly, such weeds can be classified as broad-leaf or grassy weeds. It is economically desirable to control the growth o~ such weeds without damaging beneficial plants or livestock.

Claims (30)

WHAT IS CLAIMED IS:

1. Compounds having the formula in which A and B are independently selected from hydrogen, fluorine, chlorine, bromine and methyl, provided that at least one of A or B is other than hydrogen; M is hydrogen or methyl;
X is selected from the group consisting of tri-fluoromethyl, lower alkyl having 1 to 3 carbon atoms, inclusive, nitro, chloro, bromo, fluoro, cyano, lower alkoxy having 1 to 3 carbon atoms, inclusive, trifluoro-methylthio and 2,3-diloweralkyl ureido in which each lower alkyl has from 1 to 2 carbon atoms, inclusive;
Y is selected from the group consisting of hydrogen, lower alkyl having 1 to 3 carbon atoms, inclusive, chloro, fluoro, nitro, trifluoromethyl and lower alkoxy having 1 to 3 carbon atoms, inclusive;
Z is selected from the group consisting of hydro-gen and chloro;
R1 is selected from the group consisting of hydrogen, alkyl having 1 to 6 carbon atoms, inclusive, and allyl;
R2 is selected from the group consisting of alkyl having 1 to 6 carbon atoms, inclusive, allyl, benzyl, hydroxyethyl, alkynyl having 3 to 4 carbon atoms, inclusive, N-alkylamido in which the alkyl has 1 to 3 carbon atoms, inclusive, alkoxyalkyl having 2 to 6 carbon atoms, inclusive, dialkoxyalkyl having 3 to 6 carbon atoms, inclusive, alkoxy having 1 to 4 carbon atoms, inclusive, cyanoalkyl having 2 to 4 carbon atoms, inclusive, substituted phenyl wherein said substitutent is selected from the group trifluoromethyl, dichloro and 3,3-dimethylureido;
and R1 and R2 taken together with the nitrogen is selected from the group consisting of alkyl substituted oxazolidyl wherein said oxazolidyl is substituted 1, 2 or 3 time with alkyl having from 1 to 3 carbon atoms, inclusive, morpholinyl, piperidinyl and pyrrolidinyl; and salts thereof with an acid selected from the group consisting of HCl, HBr, HI, HF, H2SO4, CCl3COOH, 2,4-dichlorophenoxy acetic acid, 3-amino-2,5-dichlorobenzoic acid, hexanoic acid, steric and naphthalene acetic acid, pivalic acid, succinic acid, 10-undecenoic acid, benzoic acid, malonic acid and maleic acid

2. A compound according to Claim 1 in which R1 is hydrogen;
R2 is alkyl having 1 to 6 carbon atoms, inclusive;
-CMAB is -CHCl2;
X and Y are independently selected from the group consisting of lower alkyl having 1 to 6 carbon atoms, inclusive and chloro;
Z is hydrogen.

3. A compound according to Claim 2 in which R1 is hydrogen;
R2 is alkyl having 1 to 6 carbon atoms, inclusive;
-CMAB is -CHC12;
X is chloro;
Y is chloro;
Z is hydrogen.

4. A compound according to Claim 3 in which R2 is isopropyl;
X is 3-chloro;
Y is 5-chloro.

5. A compound according to Claim 3 in which R2 is isopropyl;
X is 2-chloro;
Y is 3-chloro.

6. A compound according to Claim 3 in which R2 is ethyl;
X is 3-chloro;
Y is 4-chloro.

7. A compound according to Claim 3 in which R2 is n-propyl;
X is 3-chloro;
Y is 4-chloro.

8. A compound according to Claim 3 in which R2 is isopropyl;
X is 3-chloro;
Y is 4-chloro.

9. A compound according to Claim 3 in which R1 is hydrogen;
R2 is alkyl having 1 to 6 carbon atoms, inclusive;
-CMAB is -CHCl2;
X is lower alkyl having 1 to 6 carbon atoms, inclusive;
Y is lower alkyl having 1 to 6 carbon atoms, inclusive;
Z is hydrogen.

10, A compound according to Claim 9 in which R2 is isopropyl;
X is 3-methyl;
Y is 5-methyl.

11. A compound according to Claim 1 in which R1 is hydrogen;
R2 is alkyl having 1 to 6 carbon atoms, inclusive;
-CMAB is -CHCl2;

X is lower alkyl having 1 to 6 carbon atoms, inclusive;
Y is chloro;
Z is hydrogen.

12. A compound according to Claim 11 in which R2 is isopropyl;
X is 2-methyl;
Y is 3-chloro.

13. A compound according to Claim 1 in which R1 is allyl;
R2 is allyl;
-CMAB is -CHCl2;
X is chloro;
Y is chloro;
Z is hydrogen.

14. A compound according to Claim 1 in which R1 is hydrogen;
R2 is alkyl having 1 to 6 carbon atoms, inclusive;
-CMAB is -CHF2;
X is chloro;
Y is chloro;
Z is hydrogen.

15. A compound according to Claim 14 in which X is 3-chloro;
Y is 5-chloro;
R2 is isopropyl.

16. A method of controlling undesirable vegetation comprising applying to the vegetation or locus thereof a herbicidally effective amount of a compound having the formula in which A and B are independently selected from hydrogen, fluorine, chlorine, bromine and methyl, provided that at least one of A or B is other than hydrogen;
M is hydrogen or methyl;
X is selected from the group consisting of tri-fluoromethyl, lower alkyl having 1 to 3 carbon atoms, inclusive, nitro, chloro, bromo, fluoro, cyano, lower alkoxy having 1 to 3 carbon atoms, inclusive, acetyl, lower alkylthio having 1 to 3 carbon atoms, inclusive, trifluoro-methylthio and 3,3-diloweralkyl ureido in which each lower alkyl has from 1 to 2 carbon atoms, inclusive;
Y is selected from the group consisting of hydro-gen, lower alkyl having 1 to 3 carbon atoms, inclusive, chloro, fluoro, nitro, trifluoromethyl and lower alkoxy having 1 to 3 carbon atoms, inclusive;
Z is selected from the group consisting of hydrogen and chloro;
R1 is selected from the group consisting of hydrogen, alkyl having 1 to 6 carbon atoms, inclusive, and allyl;
R2 is selected from the group consisting of alkyl having 1 to 6 carbon atoms, inclusive, allyl, benzyl, hydroxyethyl, alkynyl having 3 to 4 carbon atoms, inclusive, N-alkylamido in which the alkyl has 1 to 3 carbon atoms, inclusive, alkoxyalkyl having 2 to 6 carbon atoms, inclusive, dialkoxyalkyl having 3 to 6 carbon atoms, inclusive, alkoxy having 1 to 4 carbon atoms, inclusive, cyanoalkyl having 2 to 4 carbon atoms, inclusive, substituted phenyl wherein said substituent is selected from the group trifluoromethyl, dichloro and 3,3-dimethylureido; and R1 and R2 taken together with the nitrogen is selected from the group consisting of alkyl substituted oxazolidyl wherein said oxazolidyl is substituted 1, 2, or 3 times with alkyl having from 1 to 3 carbon atoms, in clusive, morpholinyl, piperidinyl and pyrrolidinyl; and salts thereof with an acid selected from the group consisting of HCl, HBr, HI, HF, H2SO4, CCl3COOH, 2,4-dichlorophenoxy acetic acid, 3-amino-2,5-dichlorobenzoic acid, hexanoic acid, steric and naphthalene acetic acid, pivalic acid, succinic acid, 10-undecenoic acid, benzoic acid, malonic acid and maleic acid.

17. The method according to Claim 16 in which R1 is hydrogen;
R2 is alkyl having 1 to 6 carbon atoms, inclusive;
-CMAB is -CHCl2;
X and Y are independently selected from the group consisting of lower alkyl having 1 to 6 carbon atoms, inclusive and chloro;
Z is hydrogen.

18. The method according to Claim 17 in which R1 is hydrogen;
R2 is alkyl having 1 to 6 carbon atoms, inclusive;
-CMAB is -CHCl2;
X is chloro;
Y is chloro;
Z is hydrogen.

19. The method according to Claim 18 in which R2 is isopropyl;
X is 3-chloro;
Y is 5-chloro.

20. The method according to Claim 18 in which R2 is isopropyl;

X is 2-chloro;
Y is 3-chloro.

21. The method according to Claim 18 in which R2 is ethyl;
X is 3-chloro;
Y is 4-chloro.

22. The method according to Claim 18 in which R2 is n-propyl;
X is 3-chloro;
Y is 4-chloro.

23. The method according to Claim 18 in which R2 is isopropyl;
X is 3-chloro;
Y is 4-chloro.

24. The method according to Claim 18 in which R1 is hydrogen;
R2 is alkyl having 1 to 6 carbon atoms, inclusive;
-CMAB is -CHCl2;
X is lower alkyl having 1 to 6 carbon atoms, inclusive;
Y is lower alkyl having 1 to 6 carbon atoms, inclusive;
Z is hydrogen.

25. The method according to Claim 24 in which R2 is isopropyl;
X is 3-methyl;
Y is 5-methyl.

26. The method according to Claim 16 in which R1 is hydrogen;
R2 is alkyl having 1 to 6 carbon atoms, inclusive;
-CMAB is -CHCl2;
X is lower alkyl having 1 to 6 carbon atoms, inclusive;

Y is chloro;
Z is hydrogen.

27. The method according to Claim 26 in which R2 is isopropyl;
X is 2-methyl;
Y is 3-chloro.

28. The method according to Claim 16 in which R1 is allyl;
R2 is allyl;
-CMAB is -CHCl2;
X is chloro, Y is chloro;
Z is hydrogen.

29. The method according to Claim 16 in which R1 is hydrogen;
R2 is alkyl having 1 to 6 carbon atoms, inclusive;
-CMAB is -CHF2;
X is chloro;
Y is chloro;
Z is hydrogen.

30. The method according to Claim 29 in which X is 3-chloro;
Y is 5-chloro;
R2 is isopropyl.