N-(1,1-SUBSTITUTED PROPYNYL)-.alpha.-(3,5-SUBSTITUTED PHENOXY) ALKYL AMIDES AND THEIR USE AS HERBICIDES

LES N-(1,1-SUBSTITUANT PROPYNYL)-.alpha.-(3,5-PHENOXY) ALKYLAMIDES ET LEUR UTILISATION COMME HERBICIDES

English Abstract

Abstract of the Disclosure
N-(l,l substituted propynyl)- q (3,5-
substitted phenoxy) alkyl amides compounds having
the formula
<IMG>
in which R1 and R2 are independently halogen or
alkyl having 1 to 4 carbon atoms; R3 is alkyl hav-
ing 1 to 4 carbon atoms; R4 and R5 are independently
hydrogen or alkyl having 1 to 3 carbon atoms; and
their use as herbicides.

Claims

IT IS CLAIMED:
1. Compounds of the formula
<IMG>
in which Rl and R2 are independently halogen or alkyl
having 1 to 4 carbon atoms; R3 is alkyl having 1 to 4
carbon atoms, R4 is hydrogen or alkyl having 1 to 3 carbon
atom and R5 is hydrogen or alkyl having 1 to 3 carbon atoms.
2. The compound of Claim 1 in which R1 is methyl,
R2 is methyl, R3 is ethyl, R4 is alkyl having 1 to 3 carbon
atoms and R5 is alkyl having 1 to 3 carbon atoms.
3. The compound of Claim 1 in which R1 is chloro,
R2 is chloro, R3 is ethyl, R4 is alkyl having 1 to 3 carbon
atoms and R5 is alkyl having 1 to 3 carbon atoms.
4. The compoùnd of Claim 1 in which R1 is methyl,
R2 is methyl, R3 is ethyl, R4 is hydrogen and R5 is alkyl
having 1 to 3 carbon atoms.
5. The compound of Claim 1 in which R1 is chloro,
R2 is chloro, R3 is ethyl, R4 is hydrogen, and R5 is alkyl
having 1 to 3 carbon atoms.
6. The compound of Claim 1 in which R1 is methyl,
R2 is methyl, R3 is ethyl, R4 is hydrogen, and R5 is hydrogen.
17

7. The compound of Claim 3 in which R1 is chlorine,
R2 is chlorine, R3 is ethyl, R4 is methyl, and R5 is methyl.
8. The compound of Claim 2 in which R1 is methyl,
R2 is methyl, R3 is ethyl, R4 is methyl and R5 is methyl.
9. The compound of Claim 1 in which R1 is chlorine,
R2 is chlorine, R3 is ethyl, R4 is hydrogen and R5 is hydrogen.
10. The method of controlling undesirable vegetation
which comprises applying to the area where control of said
vegetative growth is desired, a growth controlling amount of
a compound having the formula
<IMG>
in which R1 ant R2 are independently halogen or alkyl having
1 to 4 carbon atoms; R3 is alkyl having 1 to 4 carbon atoms,
R4 is hydrogen or alkyl having 1 to 3 carbon atoms and R5 is
hydrogen or alkyl having 1 to 3 carbon atoms.
11. The method of Claim 10 in which R1 is methyl,
R2 is methyl, R3 is ethyl, R4 is alkyl having 1 to 3 carbon
atoms and R5 is alkyl having 1 to 3 carbon atoms.
12. The method of Claim 10 in which R1 is chloro,
R2 is chloro, R3 is ethyl, R4 is alkyl having 1 to 3 carbon
atoms and R5 is alkyl having 1 to 3 carbon atoms.
13. The method of Claim 10 in which R1 is methyl,
R2 is methyl, R3 is ethyl, R4 is hydrogen and R5 is alkyl
having 1 to 3 carbon atoms.
18

14. The method of Claim 10 in which R1 is chloro,
R2 is chloro, R3 is ethyl, R4 is hydrogen, and R5 is alkyl
having 1 to 3 carbon atoms.
` 15. The method of Claim 10 in which R1 is methyl,
R2 is methyl, R3 is ethyl, R4 is hydrogen, and R5 is hydrogen.
16. The method of Claim 12 in which R1 is chlorine,
R2 is chlorine, R3 is ethyl, R4 is methyl, and R5 is methyl.
17. The method of Claim 11 in which R1 is methyl,
R2 is methyl, R3 is ethyl, R4 is methyl and R5 is methyl.
18. The method of Claim 10 in which R1 is chlorine,
R2 is chlorine, R3 is ethyl, R4 is hydrogen, and R5 is hydrogen.

Description

. 071Z34
This invention relates to certain novel N-(l,l
substituted propynyl)-~-(3,5-substituted phenoxy) alkyl amides
which are useful as herbicides.
The compounds of the present invention are new
compositions of mat~er and correspond to the formula
~ O-C-C-N- ~ ~ECH
in which Rl and R2 are independently halcgen, ~reerably
chlorine or alkyl having 1 to 4 carbon atoms, preferably
methyl; R3 is alkyl having 1 to 4 carbon atom~, preferably
ethyl; R4 and R5 are independently hydrogen or alkyl having
1 to 3 carbon atoms, preferably methyl, more preferably both
R4 and R5 are methyl.
In the above description of the compounds of this
invention, alkyl includes both straight chain and branchet
chain configurations, for example, methyl, ethyl, n-propyl,
i~opro w l, n-butyl, sec-butyl or tert.-butyl. The term
halogen includes chlorine, bromine, iodine and fluorine.
The closest prior art known to applicants is U. S.
3,272,844.
The compounds of thi~ invention are sctive herbicides
of a general type. That is, they are herb~cidally effective
sgainst a w1te range of plant species. The method of control-
ling undesired vegetation of the present invention comprises
applying an herbicidally effective amount of the above-tescribed
compounds to the area where control is desired

~(~71Z34
An herbicide is used herein to mean a compound which
controls or modifies the grow~h of plants. By a "growth con-
trolling amount" is meant an amount of compound which causes
a difying effect upon the growth of plants. Such m~difying
effects include all deviations from natural development, for
example, killing, retardation, defoliation, dessiccation,
regulation, stunting, tillering, st~mulation, dwarfing and
the l~ke. By "plants" it is meant germinating seeds, emerging
seedlings, and established vegeta~ion including the roots and
above-ground portions.
The compounds of the present invent~on are prepared
by the following general method.
Reaction No. 1
~2 OH ~ Br~-8-OH ~ NaOH--~
Rl ~ H ~
R2 ~ 0-~3C-OH ~ NaBr
Generally, a le amount of the phenol, a slight mole
excess of the ~-bromoaIkanoic acid and about 3 moles of sodium
hydroxide are mixed in water at about 10C-15C. Then the re-
action m~xture is heated at reflux for about 2 hours. Thereafter
the mixture is cooled and tiluted with water. The pH of the
mixture is ad~usted to 8 with 19% hydrochloric acit. The solution
i8 extracted several times with ether followed by a pH ad~ustment
to 2 with 19% HCl. An oil separates which is extracted with ether.

~0'7~Z34
Evaporation of the ether after drying yields the
desired product which is asolid. The solid is purified by
recrystalization with cyclohexane.
Reaction No. 2
R2 O-¢-C-OH + Cl-C-Cl ~ ~ ¢ 8
First the acid is mixed in benzene. A small amount o
the dimethyl formamide i8 added and the slurry is heated. A
slight excess of the phosgene reactant is added to the acid
mixture in portions, The reaction is complete upon termina-
tion of HCl evolution. Evaporation of the reaction mixture
yields the desired product, a liquid.
Reaction No. 3
Rl O-~-C-Cl + H2N-C-C-CE + (C2H5)3N--~
Rl ~ O ~ ~4
R ~ R3 R5
About equal mole amounts of the amines are dissolved in
benzene. The solution is cooled to about 10C. About an equal
mole amount of the acid chloride reactant is slowly added to the
--4--

1071Z34
amine solution at a rate to maintain the temperature between 10-
15C. After the acid chloride addition is complete, the mixture
- is heated to 45-50C. for 1 hour and then is cooled to room
temperature. The mixture is diluted with H20 to dissolve the
amine hydrochloride. Some solid remains undissolved and this is
filtered. The filtrate is washed two times with 10% HCl. With
each wash more solid separate~ and it is filtered. The organic
layer i8 next washed two t~mes with 5% ~a2C03 and dried over Mg
S04 Removal of solvent leaves a solid product which is com-
bined with the solid product previously removed.
Preparation of the compounds of this invention
is illustrated by the following reaction.
Example
Preparation of N-(l,l dimethyl propargyl)-~ -(3,5-dichlorophenoxy)
butvramide
Cl ~ ~ U CIH3
~ OCH C - N - IC - C'CH
Cl CH2CH3 CH3
100.0 g. (0.614 moles) of 3,5-dichlorophenol and
112.5 g. (0.675 moles) of ~-Bromobutyric acid are mixed and
100 ml. of water is added. The mixture i8 cooled to 10C. in
an ice wster bath and 147.2 g. (1.842 moles) 50Z NaOH i8
added dropwise over lO-15C. The reaction mixture is wanmed
to room temperature and then heated at reflux for two hours.
A~ter cooling, the mixture i8 diluted with H20 to 600 ml.ant
the pH is ad~usted to 8 with 19% HCl. The aqueous solution
is extracted 3 times with 150 ml.portions of ether and is then
ad~usted to pH 2 with 19% HCl. An oil separates which is

1C~7~234
extracted with ether. Evaporation of the ether after drying
leaves a white solid, 94.3 g., m.p. 102-108C. This solid is
recrystalized from 250 ml. cyclohexane to give 71.8 g. ~ -(3,5-
dichlorophenoxy) butyric acid m.p. 113-116C.
71.8 g. (0.288 moles) of ~-(3,5-dichlorophenoxy)
butyric acid and 75 ml. of benzene are placed in a 500 ml. flask
to which a dropping funnel with dry-ice condenser is attached.
The slurry is stirred and the 0.2 ml. dimethyl formamide is
added. The mixture is heated to 35C. and 10 g. of phosgene is
condensed into the mixture to initiate reaction. The start
of the reaction is evidenced by HCl evolut~on and foaming.
26.0 g. more phosgene is added in 5 gm. increments. At the
conclusion of the reaction (HCl evolution ceasing), the
reaction mixture is evaporated leaving a re9idu`al1iquid
C~-(3~5-dichlorophenoxy) butyryl chloride 77.6 g., N20 - 1.5345
164 g. (1 63 les) triethyl amine and 132 g. (1.58
mole8) 3-methyl-3-amino-1-butyne àre dissolved in 1300 ml.
benzene and the solution is cooled to 10C. in an ice water bath.
412.9 g. (1.55 les)c~-(3,5-dichlorophenoxy) butyryl
chloride diluted with 200 ml. benzene is added dropwise to the
amine 801ution. Periodic additions of benzene (400 ml.) are
made in order to adequately stir the mixture. After acid
chloride addition is complete, the mixture is heated to 45-50C.
for 1 hour more and then allowed to come to room temperature
overnight. The mixture is diluted with lO00 ml. H20 to dissolve

~07~234
the amine hydrochlor~de. Some solid remains undissolved and
th~s i8 filtered. The filtrate is washed two t~mes with 1000 ml.
10% HCl. With each wash more solid separates and it is
filtered. The organic layer is next washed two times with 5%
Na2C03 and dried over Mg S04. Removal of solvent leaves 377 g.
which is combined with the previously removed solid to yield
436 g, of the desired product, m.p. 90-94C.
The foll~wing is a table of certain selected
compounds that are preparable according to the procedure
described hereto. Compound numbers are assigned to each
compound and are used through the remainder of the application.
Table I
~2 ~ O-~-C-N-~ C--CH
Compound 4 5
Number Rl R2 R3 R R
1 CH3 CH3 CH3 CH3 CH3
2 a) Cl Cl CH3CH2 CH3 CH3
3 CH3 CH3 ' CH3CH2 CH3 CH3
4 Cl Cl CH(CH3) 2 CH3 CH3
Cl Cl CH3CH2cH2 CH3 CH3
6 Cl Cl CH3CH2 H H
7 CH3 CH3 CH3CH2 H H
a) Prepared in Example 1.

1071234
Herbicidal Screenin~ Tests
As previously mentioned, the herein described
compounds produ~ed in the above-described manner are phyto-
toxic compounds which are ~eful and valuable in controlling
various plant species. Selected compoundsof this in~ention
are tested as herbicites in the follow~ng manner.
Pre-emergence herbicide test. On ~he day pre-
ceding treabment, seeds of seven different weed specie~ are
planted in individual rows using one species per row across
the width of the flat. The seeds used are hairy crabgrass
(Digitaris san~u~nalis (L.) Scop.), yellow foxtail (Setaria
~lauca (L ) Beauv.), watergrass (Echinochloa crusgalli (L.)
Bea w .), California red oat (Avena sativa (L.), redroot
pigweed (Amaranthus retroflexu~ (L ) Indian mustard (Brassica
1uncea (L.) Coss.) and curly dock (Rumex crispus (L.). Ample
seeds are planted to give about 20 to 50 seedlings per row,
after emergence, depending upon the size of the plants.
The flats are watered after planting. The spraying solution is
prepared by dissolving 50 mg. of the test compound in 3 ml.
of a solvent, ~uch as acetone, containing 1% Tween 2 ~
(polyoxyethylene sorbitan monolaurate). The following day
esch flat is sprayed at the rate of 20 pounds of the candidate
campound per 80 gallons of solution per acre. An atomizer is
used to spray the solution onto the soil surface. The flats
are placed ln a greenhouse at 80F. and watered regularly.
Two weeks later the degree of weed control i9 tetermined
by comparing the amount of germination and growth of each
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~07~Z34
weed in the treated flats with the same weeds in several un-
treated control flats. The rating system is as follows:
- - no significant injury (0-15 percent control)
+ ~ slight injury (25-35 percent control)
++ ~ moderate injury (55-65 percent control)
lll = severe injury or death (85-100 percent control)
An activity index i~ used to represent the total
activity of all seven weed species. It is the sum of the
number of plus marks, so that an activity index of 21
represents a~most complete control of all seven weeds. The
result~ of this test are reported in Table II.
Post-emergence herbicide test. Seeds of five weed
species including hairy crabgrass, watergrass, California red
oats, Indian mu~tard, and curly dock and one crop, pinto beans
(Phaseolus vulgaris), are planted in flats as described above
for pre-emergence screening. The flats are placed in the
greenhouse at 72-85F. and watered daily with a sprinkler
About 10 to 14 day~ after planting when the pr~mary leaves
of the bean plant are a~most fully expanded and the first
trlfoliate leaves are ~ust starting to form, the plants are
sprayed. The spray ls prepared by weighing out 50 mg. of
the test compound, dissolving it in 5 ml. of acetone con-
taining 1% Tween 2 ~ (polyoxyethylene sorbitan monolaurate)
and then addlng 5 ml. of water. The solution is sprayed on
the foliage using an atomizer. The spray concentrat~on is
0.5% and the rate would be approx~mately 20 pounds per acre
if all of the spray was retained on the plant and the soil,

107~Z34
but some spray is lost so it is est~mated that the applica-
tion rate is approx~mately 12.5 pounds per acre.
Beans are used to detect defoliants and plant
growth regulators. The beans are tr~mmed to two or th~ee
plants per flat by cutting off the excess weaker plants
several days before treatment. The treated plant~ are placed
back in the greenhouse and care is taken to avoid sprinkling
the treated foliage with water for three days after treatment.
Water is applied to the soil by means of a slow stream from a
watering hose taking care not to wet the foliage.
In~ury rates are recorded 14 tays after treatment.
The rating 9ystem is the same as described above for the pre-
emergence test where (-), (~ +), and (lll) are used for
the different rates of injury and control. The injury symptoms
are also recorded. The maximum activity index for complete
control of all the species in the post-emergence screening
test is 18 which represents the sum of the plus marks obtained
wlth the 9iX plant 9pecies used ln the test. The herbicide
activity is shown in Table II.
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~071Z34
- TABLE II
HERBICIDAL ACTIVITY
SCREENING RESULTS
Herbicidal ActivitY Index**
Compound Pre-~mer~ence Post-emergence
Number (20 lb7A) (12.5 lb/A)
1 21 i7
2 21 15
3 21 15
4 12 3
18 13
6 20 15
7 21 15
** 21 - 85-100% control of all seven plant species tested
pre-emergence.
18 - 85-100% control of all six plant species tested
post-emergence.
The compounds of the present invention are used as
pre-emergence or post-emergence herbicides and are applied in
a variety of ways at various concentrations. In practice,
the compounds herein defined are formulated into herbicital
composition~, by admixture, in herbicidally effective amounts,
with the ad~uvants and carriers normally employed for facili-
tating the disper~ion of act~ve ingredients for agricultural
applications, recognizing the fact that the formulation and
mode of application of a toxicant may affect the activity of the
materials in a given application. Thus, these active herbicidal
compounds may be formulated as granules of relatively large
particle size, as wettable powders, as emulsifiable concen-
trates, as powdery dusts, as ~olutions or as any of several
other known types of fonmulations, depend~ng upon the desired
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107~Z34
mode of application. Preferred fonmulations for both pre- and
post- emergence herbicidal applications are wettable powders,
emulsifiable concentrates and granules. These formulations
may contain as lit~le as about 0~5% to as much as about 95%
or more by weight of active ingredient. The amount applied
depends upon the nature of the seeds or plants to be controlled
andthe rate of application varies from ~8 to approximately 50
pound~ per acre.
Wettable powders are in the fonm of finely divided
particles which di~perse readily in water or other dispersant.
The wettable powder i~ ultimately applied to the soil either
as a dry dust or as a dispersion in water or other liquid.
Typical carriers for wettable powders include fuller's earth,
kaolin clays, silicas and other readily wet organic or
inorganic diluents. Wettable powders normally are prepared to
contain about 5% to about 95% ofthe active ingredient by
weight and usually also contain a small amount of wetting,
dispersing or emulsifying agent to facilitate wetting and
dispersion.
Emulsifiable concentrates are homogeneou~ liquid
compositions which are dispersible in water or other dispersant,
and may consist entirely of the active compound with a liquid
or solid emulsifying agent, or may also contain a liquid
carrier, quch as xylene, heavy aromatic naphthas, isophorone
and other non-volatile organic solvents. For herbicidal appli-
cstion, these concentrates are dispersed in water or other
liquid carrier and normally applied as a spray to the area to
be treated. The percentage by weight of the essential active
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1071Z34
ingredient may vary according to the manner in which the
composition is to be applied, but in general comprises about
0.5% to 95% of active ingredient by weight of the herbicidal
composition.
Granular formulations, wherein the toxicant is carried
on relatively coarse particles, are usually applied without
dilution to the area in which suppression of vegetation is
desired. Typical carriers for granular formulations include
sant, fuller's earth, bentonite clays, vermiculite, perlite
and other organic or inorganic materials which absorb or which
may be coated with the toxicant. Granular formulations
normally are prepared to contain about 5% to about 25% of
active ingredient and may also contain small amounts of other
ingredients which may include surface-active agents such as
wetting agents, dispersing agents or emulsifiers; oils such as
heavy aromatic naphthas, kerosene or other petroleum fractions,
or vegetable oils; ant/or stickers such as dextrin~, glue or
synthetic resins.
Typical wetting, disper9ing or emulsifying agents
used in agricultural formulations include, for example, the
alkyl and alkylaryl sulfonates and sulfates and their sodium
salts; polyhydric alcohols; and other types of surface-active
agents, many of which are av~able in commerce. The surface-
active agent, when used, normally comprises from 0.1% to 15%
by weight of the herbicidal composition.
Dusts, which are free-flowing admixtures of the
active ingredient with finely divided solids such as talc,
clays, flours, and other organic and inorganic solids which
act as dispersants and carriers for the toxicant, are useful
formulations for soil-incorporating applications.

~07~Z34
Pastes, which re homogeneous suspensions of a
finely divided solid toxicant in ~ liquid carrier such as
water or oil, are employed for specific purposes. These for-
mulations norm2lly contain about 5% to about 95% of active
ingredient by weight, and may also contain small amounts of
a wetting, dispersing or emulsifying agent to facilitate dis- ~ -
persion, For application, the pastes are normally diluted and
applied as a spray to the area to be affected.
Other useful fonmulations for herbicidal applica-
tions include s~mple solutions of the active ingredient in
a dispersant in which it is completely soluble at the desired
concentrat~on, such as acetone, alkylated naphthalenes,
xylene or other organic solvents. Pressurized sprays, typically
aerosols, wherein the active ingredient is dispersed in finely-
divided form as a result of vaporization of a l~w boiling
di~persant solvent carrier, such as the Freons, may also be used.
The phytotoxic compositions of this invention are
applied to the plants in the conventional manner. Thus, the
du~t and liquid compositions can be applied to the plant by
the use of power-dusters, boom and hand sprayers and spray
du ters. The compositions can also be applied from airplanes
as a dust or a spray because they are effective in very low
dosages, In order to modify or control grGwth of germinat~ng
~eeds or emerging seedling~, as a typical example, the dust and
liquid compositions are applied to the soil according to con-
vention methods and are distributed in the soil to a depth of
at least 1¦2 inch below the soil surface, $t is not necessary
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_, ~

107~234
that the phytotoxic compositions to be admixed with the soil
particles since these compositions can also be applied
merely by spraying or sprinkling the surface of the soil.
The phytotoxic compositions of this invention can also be
applied by addition to irrigation water supplied to the
field to be treated. This method of application penmits
the penetration of the compositions into the soil as the
water i~ absorbed therein. Dust compositions, granular
compositions or liquid formulations applied to the surface
of the soil can be distributed below the surface of the
80il by con~entional means such as discing, tragging or
mixing operations.
The phytotoxic compositions of this invention can
also contain other additaments, for example, fertilizers,
pesticides and the like,used as ad~uvant or ~n combination
with any of the above-described adjuvants. Other phytotoxic
compounds useful in combination with the above-described
compounds include, for example, 2,4-dichlorophenoxyacetic acids,
2,4,5-trichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxy-
acetic acid and the salts, esters and amides thereof; triazine
derivatives, such as 2,4-bis(3-methoxypropylamino)-6-methylthio-
s-triazine, 2-chloro-4-ethylEmino-6-isopropylamino-s-triazine,
and 2-ethylsmino-4-isopropylamino-6-methylmercapto-s-triazine;
urea derivatives, such as 3-(3,4-dichlorophenyl)-1,1-dimethyl
urea and 3-(p-chlorophenyl)-1,1-dimethyl urea: and acetsmides
such as N,N-diallyl-O~-chloroacetamide, and the like;
benzGic acids such as 3-amino-2,5-dichlorobenzoic; thio-
carbamates, such as S-propyl d~propylthiocarbamate, S-ethyl-
dipropylthiocarbamate, S-ethyl cyclohexylethyl thiocarbamate,

1071Z34
S-ethyl hexahydro-lH-azepine-l-car~othioate and the like;
4-(methylsulfonyl)-2,6-dinitro-~,N-substituted anilines, such
as 4-(methylsulfonyl)-2,6-dinitro-N,N-di-n-propyl aniline,
4-trifluoromethyl-2,6-dinitro-N,~-substituted anilines, such
as 4-trifluoromethyl-2,6-dinitro-N,N-di-n-propyl anilihe and
4-trifluoromethyl-2,6-dinitro-N-ethyl-N-n-butyl aniline.
Fertilizers useful in combination with the active ingredients
include, for example, ammonium nitrate, urea and superphosphate
Other useful additaments include materials in which plant
organisms take root and grow such as compost, manure, humus,
sand and the like.
The concentration of a compound of the present
invention, constituting an effective amount of the best mode
of atministration in the utility disclosed is readily deter-
minable by those skilled in the art.
-16-