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Патент USA US3095309

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United States Patent “O "2'
Patented June 25, 1963
‘~ever,.thecompositions of the invention will contain from
‘about 0.20 to ‘1‘61parts ‘by weightof thiolca'rbamate for
_ r
to‘I. ‘tlu ‘Pont de ‘Nemours and 'Corirpanypwilniing
~eachgp'art1by weight ofdaryl rtalkyleurea. Interm‘s of pro
;plortions,‘thelrelative amountso'f each respective herbicidal
ton, "Del.,'a corporation ofnDelaware
"component can be said to be-‘from about 16:1 to 1:5, the
Raymond vW. .Luckenbaug’h, 'Wilniington, .,Del., assignor
‘No Drawing. JFiled \May ‘11, -19_60,~Ser.’ No.~"<28,‘191
Z-"Clziims. ~(Cl. '71—2~.‘6‘)
ratios indicating the amount of'thiolearbamate-to ‘sub
"This invention relateslto . the ‘discovery'that a- combina
- .tion’ of ‘at: least one herbicidal aryl .alkyl- urea-.withc'certain
.xesters ‘of ‘thiolcairbamic . acid ‘derivatives :surprisingly 1“ has
ofthe ‘invention, = comprising herbicidal aryl alkyl urea
stituted urea.
il‘t-lis much- preferred to‘ifonnulatethe active components
1 compounds and ~thiolc'ai1bamates ~With conventional ; pest
~-control1adjuvan-ts,~modi?ers, or diluents,‘ hereinafter called
inert carriers, because handling is facilitated, and herbicidal
herbicidal power not possessedftby either. componentrem
.1 ployed separately.
» action ‘> is thereby frequently? enhanced. ‘ Such herbicidal
:1 have found that ;mixtures ‘of jhenbicidal ‘aryl ialkyl
occur-positions ‘oriformulationss areprepared in the, form of
ureas with certain esters of thiolcarbamic acid ‘derivatives 15 powdered solids, granules, or, liquids.
give "sunpri‘singherbicidal results. ‘ These combinations are
These compositions, “whether solutions, "emulsions, dis
.‘more‘ effective as Weed 'killers'than either ‘herbicidal. \c'o'n'i
persions of the active components in a liquid solvent, or
-.p0n'ent used valone at 1 equivalent rates. .These combina
'wettablepowders, often'have as an'inert. carrier one or
-;tions arev ‘superiorin that they‘control Iawider variety of
‘more of thesurface-active agents in amounts .su?icient to
. broadleaf and grass weeds.
render 1a given ‘composition containing‘the ‘active vcom
This enhanced effectiveness is panticularlytoutstanding
fponentrea‘dily dispers‘ible in water or in oil. By the term
in the case;of;-pre-emergence control of weedsin crop
“surface-active agent” it‘ is understood that wetting agents,
.areas becausethe. crops are tolerant to these ;cornbina
vdispersing agents, suspending agents, and emulsifying
tions when .theyare applied at-low dosage rates thatare
uagents‘are included.
sut?cient to give Weed control.
,Suitable‘surface-active agents. are ‘set out, for example,
The herbicidal aryl alkyl ureas ‘employedinicomp‘osi
in ‘Searle U.S.. ‘Patent No._ 2,426,417, Todd US. Patent
tionsan'd processes of the invention can befenu'r'on (1,1
No. 2,655,447, ‘Jones U.S. Patent No. 2,412,510, or
.dirnethyl - 3 1phenylurea), monuron ,(1,~1 - dimethyLS-p
‘Lenher U.S. ‘Patent No. 2,139,276. A detailed list of
chlonophe‘nylurea'), diuron (1,1-tlimethyl#31(3.,4-dichloro
‘such ‘agents is'set5forth in an article in “Soap and Chemical
,phenyl)urea), neburon (3 - (3,4 - dichlorophenyl) -'1 -"n
Specialties,” vol. 3‘1,"No. ‘7,.p‘ages 50—'6,'1;‘No. ‘8, pages
48:61; No. ,9, pages '52-'67; ‘and .No. 10,,pages 38-67
butyl-l-methylurea) , ‘or any of these llT'WhiChjOHG methyl
group" is'repllaced by a methoxy group, ‘namely l-methoxy
(1955); see also McCutcheon, “Chemical Industries,”
'N'overnber“1947, page ‘8011, entitled “Synthetic Deter
<1-rnethyli3-phenylurea, 1 - methoxy-lamethyle3-pichloro
phenyl-urea, or l-me‘thoxy-1-methyl-3-(3,4-dichlorophen
The thiolcar-bamic acid. derivatives used are of ‘the
gents,” and. Bulletin E—607 of the Bureau of ‘Entomology
and" Plant Quarantineof the U.S.. Department of, Agricul
ture. :In'general, less 1th'an.10% ‘by weight of surface
active. agent ‘is, present .in the compositions of the inven
vtionzatnd the amount of .surfaceya‘ctive agent in any given
40 composition can'jbe. as low :as 1 %, or even less.
‘where R1, R2, and R3 are alkyl radicals 'containing‘i2, "3,
TPoyv-der'ed or {dust compositions of ‘the invention,
Whether or not ‘also modi?ed with asurface-active agent,
are prepared
‘the active ,compoundsof the _in
. or 4 carbon‘atoms.
ventioh'with‘?nely divided-inert carriers. Such, carriers
Illustrative of 'thiol'carbamic ‘acid derivatives which can 45 aregpreferably tale, 7 natural _ clays, ,_ pyrophyllite‘, diatoma
be used‘ ‘are:
ceousearth and'_?ours such asrwalnu‘t ‘shell, vvhe‘at, soya,
N,N-di(n-propy1) thiolcarbamic acid, ethyl ester
'N-i ('n-butyl') LN-ethylthidIcarbarni'c acid, naprop-yliester
‘N,N-:di (n-pnopyl) thiolcarb amic acid, n=propyliester
‘N-(nrbuityl)iN-ethylthiolcarbamic acid, ethyl ester
>N,N:dietl1yl thiolcarbamic acid, en-butvltester
In operating in. accordance with ‘the. present invention,
‘redwood and cotton seed‘flours. Other inert solids which
_ can be used include magnesium,._ealciumicarbonates, cal
ciu'r'nl phosphates, sulfur, lime, etc., either _'in_po,wder or
'in granular form. The. Percentagesfby Weight of theactive
components of the invention and the powdered or dust
compositions of theiinvention will vary; according to the
‘manner in which the composition islto be, applied, but in
any suitable amount of herbicidal .aryl alkyl‘urea "can-line
general willfbe, from ab'out_0.1 to-95- percent by weight of
employed in ‘combination with the thiolcar-bamate to 'ob 55 the‘herbicidalcomposition.
tain compositionslin which the tvvohenbicid-al ‘components
Herbicida1 compositions containing the components of
are ‘mutually: activating. The relative pnopontionseof ‘the
‘ the‘_ invention can also be ‘prepared by dispersing the
active ‘comp onents‘ will ‘vary depending upon the; particular
compositions ‘in an inert nonaqueous carrier. Aliphatic
aryl .alkyl urea employed, {the t v‘plant species “to _-be 1. con
and . aromatic hydrocarbons, for‘ example, hydrocarbons
trolleduthe physiological ‘age of the plantspthe prevailing 60 .0'f;pet1‘oleurn origin, are preferred as carriers. These dis
.climaticconditions, etc. -It is impossible, therefore,,to
epersion's, are prepared by, milling‘jthe ,-c0rnpositions_of the
‘state.- exactly the proportionsthatwwill be usedin all ,situ
invention withdis'pering agents and-suspending agents
ration-stand, indeed,<the exact amounts of toxicantsjin
“andthetinértvliqu-idkcarriers inniills suchiasipebble mills.
the mixture do notappear-to be. critical. In general, how
.The, amount of the herbicides in the dispersion can range
from 10% or less to 40 or even 50 percent by weight
composition or with a powdered solid to give a dust con
of the oil dispersion.
Adhesives such as gelatin, blood albumen, resins, for
example, rosin, alkyd resins and the like, can also be
taining relatively low concentrations of active compounds.
used in certain compositions to increase retention or
to 95 percent by weight of the combined herbicidally
tenacity of deposits following application.
active components.
Compositions of the invention may be prepared in vari
The herbicidal compositions as applied in the form of
a spray or a dust will contain from about 0.02 percent
For pre-emergence use the rate of
application of active components of the invention will
ous ways as follows:
range from about 0.25 to 5 pounds per acre for her
Wettable powders are prepared by combining in a
blender the two active components in the desired ratio
together with a ?uf?ng diluent as a grinding aid, a wetting
bicidal aryl alkyl urea compounds in the compositions of
the invention. For general ‘long-term weed control, such
agent to assure easy preparation of an aqueous suspen
sion and also a dispersing agent to prevent ?occulation
in water. These components are blended together, then
as on industrial sites, one might choose to use rates as
high as 50 pounds per acre of the combined active ma
terials. Of course, the thiolcarbamates will be in these
formulations according to the ratios expressed earlier.
passed through a hammer mill or other suitable grinding 15 Certain particular usage rates, such as 0.25 to 2 pounds
device until the particle size is substantially all below
50 microns. The product is then reblended until homo
Aqueous dispersions are prepared by mixing the active
components, a dispersing agent, and a suspending agent 20
with water and grinding in a pebble mill or sand mill
until the insoluble particles are substantially all below 5
Oil dispersions are prepared in substantially the same
per acre, are preferred for some crop uses.
It must be
understood that the determination of the proper rate in
any given instance is conventional procedure to those
skilled in the art of pre-emergence weed control.
Pre-emergence applications of these compositions give
effective weed control for large variety of weed species
with a good safety factor for crops. For example,
seedling broadleaf weeds, germinating nuts edge and
grasses are more effectively controlled by this mixture
way as aqueous dispersions, but in this case the dispersing 25 than they are by either component used alone in total’
agent chosen is also an emulsi?er for the oil so that the
equivalent amounts.
The mixtures are used for weed control in corn, al
?nal product can be diluted with water to form a spray
falfa, cotton, potatoes, sugarcane, ?ax and strawberries.
Granules are prepared by spraying an aqueous sus
For example, 2 pounds per acre of neburon in combina
pension-emulsion of the two active components upon a 30 tion with 2 pounds per acre of N,N-dipropylthiocarbamic
granular diluent such as granular attapulgite While tum
acid, ethyl ester gives effective weed control with no in
bling the latter to obtain uniform deposition. Alterna
jury to alfalfa.
tively, granules may also be prepared by blending a
Some variation in application rates will be caused by
powdered form of the solid active material with attapul
the particular type of soil involved in pre-emergence ap
gite or calcium magnesium bentonite, moistening the mix, 35 plications. Thus, more highly adsorptive soils can have
granulating, and drying, followed by impregnation with
applied to them higher rates of active components of the
the liquid active material by spraying on the dry granules.
invention Without affecting crop tolerance to the com
Dusts are most frequently prepared by diluting wettable
binations. In general, however, the rates of application
powders with a dense, rapid settling diluent such as
rnicaceous talc by blending the two together in a ribbon 40 will be those expressed above for ‘the combinations of
or cone blender. Alternatively, where wetting and dis
persing agents are undesirable, the active components are
?rst mixed with a minor amount of a ?ufiing diluent as
the invention.
vIn order that the invention can be better understood,
the following examples are given in addition to the ex
amples already given above. The examples illustrate
a grinding aid, micropulverized and then blended with
45 typical herbicidal compositions of the invention, methods
the dense major diluent.
The herbicidal compositions are applied as sprays,
for their preparation, herbicidal applications, and the re
dusts or granules to the locus or area to be protected
sults obtained. The numbers following the tabulated in
from weeds. Such application can be made directly upon
gredients represent parts by weight of the ingredients in
the locus or area to be protected ‘and the weeds thereon
the respective compositions unless otherwise noted.
during the period of weed infestation in order to destroy 50
the weeds, or, alternatively, the application can be made
in advance of an anticipated weed infestation to prevent
Granular formulations:
such infestation. Thus, the compositions can be applied
as aqueous foliar sprays or as sprays directly to the sur
N,N - dipropylthiolcarbamic
face of the soil. Alternatively, the dry powdered or 55
granulated compositions can be applied directly on the
3-phenyl-1,1-dimethylurea (fenuron)
plants or on the soil. For some purposes it will be con
Granular 15~30 mesh attapulgite _________ __ 99.0
____________________________ __
_____ __
venient to use granular forms of the compositions such as
In the preparation of the above composition, ?nely
in the treatment of pond and lake bottoms or in the treat
ment of vegetation where it is desirable to get the com 60 ground fenuron is suspended in vwater as a 10% aqueous
suspension. N,N-di(n-propyl)thiolcarbamic acid, ethyl
position on the soil surface without depositing it on the
plant foliage.
ester is dissolved in acetone to yield a 10% solution.
The active ingredients are, of course, applied in
Granular attapulgite, 15~3>0 mesh, is placed in a revolv
ing drum and well agitated. It is sprayed, from separate
The amount of herbicidally active compounds present in 65 nozzles, with the solution of N,N-di(n-propyl)thiolcar
the compositions as actually applied for destroying or
bamic acid, ethyl ester and the suspension of fenuron so
preventing Weeds will vary with the herbicidal activity
that 8 pounds of the solution and 2 pounds of the sus
of the active ingredients, the purpose for which the ap
pension are applied per 100 pounds of attapulgite. The
plication is being made (i.e., whether for short-term or
long-term control), the manner of application, the par 70 resulting granular product is dried, then applied with a
amounts sufficient to exert the desired herbicidal action.
ticular weeds for which control is sought, and like var
iables. Thus, if highly active ingredients are to be used
for the control of weed infestations that plague food crops,
the compositions containing the active ingredients are
normally further diluted with a liquid to form a spray 75
fertilizer spreader at a rate of 250 pounds per acre. This
is used as a pre-emergence treatment for weed control in
cotton on certain soils. This controls weeds such as
Johnson grass, crab grass, foxtail, lamb’s quarters, chick
weed, rough pigweed, mustard, and velvet leaf.
13,,‘ 095,299
Granular formulation:
N-butyl-iN-ethylthiolca‘rlbaniic :acid, Pn-propyl
ester .._
(diuron) ________________________ __.__-..__ .15
N,-N-dipropyl thiol'carbamic acid, n-propylester__ 2'5
3 -. (3,‘,‘4 -.'dichlorophenyl) -"’1 - n'-‘b.ntyl-1-methy1
..urea _.'(neburon)_____‘_________________ __
3 t- 1 (3,14 / - .dichlorophenyl) » - r1,~1 -- .dimethylurea
Alcolated naphthalene (principally alpha methyl
‘ Granillar‘l‘S-"FU mesh ‘attapuljgite _______ _'____ ‘98.0
_________________________ __ 55
Alkyl aryl polyether alcohol _______________ __
{A ,rgrann‘lar ,formulation containing :the above
"IIhiswcomposi-tion r-is prepared by :simply mixing-the
ponents is prepared in the manner described in Example 1.
-It is applied with a fertilizer spreader at a rate of ‘20
components. It is emulsi?ed-‘sin mater 'r?oraapplication.
pounds per acre to sweet corn. Effective control of grass
When applied at a rate of 3 pounds per acre of the herbi
cidal urea and 5 pounds per acre of the thiolcarbamate,
excellent weed control is obtained in sugar cane ?elds.
and 'broadleaf ‘weeds is obtained without injury to the
Example 3
Control of seedling Johnson grass, crab grass, foxtail, pig
Percent 15 weed, and lamb’s quarters is attained. Severe retarda
3 - (parachlorophenyl) - 1,1-dimethylurea (mon
tion of ‘nut sedge is noted.
_______________________________ __
Example 7
N,N-dipropylthiolcarbamic acid, ethyl ester
Attapulgite _____________________________ __ '20
Micaceous talc
3 - (3,4 - dichlorophenyl) - l - n - butyl - 1
:methylurea (nebu-ron) _________________ __
NgN-dipnopyl thiolcar-bamic acid, ethyl ester--- 2.5
The monuron, N,\N-di(n-propyl)thiolcarbamic acid,
Granular attapugite _____________________ __ 95.0
ethyl ester and attapulgite are ?rst blended and ground
These granular compositions are prepared in the same
through a micropulverizer, then reblended with micaceous 25 manner
as described in Example 4 and they are applied
tale. The composition is applied with :a dust spreader at
'by hand at a rate of 100 pounds per acre. They control
50 pounds per acre. This is used as a treatment for weed
annual grasses and Ibroadleaf weeds around ornamental
control in asparagus. It is applied before the seedlings
plants, such as yelws, arborvitae, p?tzer juniper and black
emerge or before spears emerge in the spring.
spruce, without injury.
Similar results are obtained when one replaces the 30
monuron of Example 3 with an equivalent amount of
Wettable powder:
3-(3,4 — dichlorophenyl) - 1,1 - dimethylurea (di
1N,n-butylJN-ethylthiolcarbamic acid, n-propyl
___ 9.38
N,N-dipropylthiolcarbamic acid, ethyl ester
3 - (p-arachlorophenyl) - 1,1 - dimethylurea (mo
Example 4
Example 8
Micaceous talc
___________________________ __ 25.00
The monuron, N,N-di(n~propyl)thiolcarbamic acid
Alkyl naphthalene sulfonic acid, sodium sol__ 1.50 40 ethyl ester and a-ttapnlgite are first blended and ground
through a micropulverizer, then reblended with micaceous
Low viscosity methylcellulose ___________ __ 0.30
tale. The composition when applied at a rate of 100
The above composition is prepared by blending the
pounds per acre to a plowed ?eld retards nut sedge growth
components together in a ribbon blender, micropulveriz
and germinating broadleaf weeds.
ing and reblending. This composition is extended in 45 This application is a continuation-in-part of my appli
water and sprayed at a rate of 3/4 pound per acre of diuron
cation Serial No. 805,732, ?led April 13, 1959, now
and 2 pounds per acre of N,N-di(n-propyl)thiolcarbamic
.Diatomaceous silica ___________________ __ 63.82
abandoned, which in turn is a continuation-impart of
Serial No. 726,328, ?led April 4, 1958, and now aban~
nual broadleaves and grasses is obtained. Some retarda 50 The invention claimed is:
tion of nut sedge growth is noted. The corn is tolerant
11. A herbicidal composition comprising a herbicidally
to combinations of this type.
effective amount of a compound selected from the group
N-ethyl-N-n-butylthiolca-rbamate, n-propyl ester can
consisting of 1,1~dimethyl-3~phenylurea, 1,1-dimethyl-3
also be used in the above example in place of the N,N-di
p-chlorophenylurea, 1,1 - dim-ethyl-B-(3,4-dichlorophenyl)
propylthiolcarbamic acid, ethyl ester. Annual weeds in 55 urea, 3-(3,4~dichlorophenyl)-1-n-butyl-1-methylurea, l
acid ethyl ester, as a pre-emergence treatment to a ?eld
sown with corn. Excellent control of germinating an
crops such ‘as peanuts, corn, and green beans are con
methoxy-l~methyl-3-phenylurea, l - methoxy-l-methyl-3
Similar results can also be obtained by replacing the
diuron of the above example with an equivalent amount
of -3-(3,4-dichlorophenyl)dl-methoxyql-methylurea.
Example 5
p-chl-orophenylurea, and 1-methoxy-l-methyl-3-(3,4-di
ch1orophenyl)urea in admixture with a herbicidally effec
tive amount of a compound selected from the group con
60 sisting of compounds of the formula
3 - (3,4 - dichlorophenyl) - 1 - methyl - 1 - n - bu
tylurea (neburon) ______________________ __
N,N-dipropyl thiolcarbamic acid, ethyl ester
where R1, R2, and R3 are :alkyl radicals containing from
2 through 4 carbon atoms.
Granular attapulgite ______________________ __ 98
The above composition is prepared as a granular as
described above in Example 1. This composition is ap
plied at a rate of 200 pounds per acre as a pre~emergence
of 1,‘1ddi-methyl-il-phenylurea, 1,1-dimethyl-3-p-chloro
phenylurea, :1,1-dimethyl-3-(3,4~dichlorophenyl)urea, 3
treatment in alfalfa and strawberries. This controls
annual weeds during the growing season, especially such
weeds as pigweed, annual bluegrass, ch-ickweed, wild mus
tard, crab grass and foxtail.
2. A process for the control and destruction of weeds,
which process comprises applying, to a locus to be pro
tected, a composition comprising a herbicidally effective
amount of a compound selected from the group consisting
(3,i4-dichlorophenyl)-1~n-butyla1-methylurea, l-methoxy
l-methyl-S-phenylurea, t1~methoxy-ldmethyl-3-p-chloro
References Cited
phenyl‘urea, and 1-methoxy-1-methy1-3-(3,4-diohlorophen
yl)urea in admixture with a herbicidally effective amount
of a compound selected from the group consisting of com
pounds of the formula
where R1, R2, and R3 ‘are valkyl radicals containing from V
2 through 4 carbon atoms.
the ?le of this patent
Ryker et a1 ____________ __ May 31, 1955
Tilles et a1. __________ __ Nov.
Tiiles et a1 ____________ __ Nov.
Tilies et a1 ____________ __ Nov.
Schercr et :al ___________ __ Nov.
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