IMPROVED COMPOSITIONS FOR NEMATODE CONTROL

COMPOSITIONS AMELIOREES SERVANT A LUTTER CONTRE LES NEMATODES

English Abstract

The present invention provides novel compositions, unexpectedly advantageous
for controlling nematode, insect or acarid infestation of a plant, comprising
a quantitatively variable combination of a compound of formula (I) in
combination with selected adjuvants from among the typical wetting, dispersing
or emulsifying agents, preferably, for example Tergitol.

French Abstract

L'invention concerne des compositions nouvelles présentant des avantages inattendus et servant à lutter contre les agressions occasionnées à des plantes par des nématodes, des insectes ou des acariens. Ces compositions sont constituées par une combinaison quantitativement variable d'un composé représenté par la formule (I) et d'adjuvants sélectionnés parmi des agents typiques d'humidification, de dispersion ou d'émulsion, tels que de préférence Tergitol?.

Claims

38
CLAIMS
1. A composition comprising a combination of a compound of the formula
(I)
<IMG> I
wherein:
n=1,3,6,7,9,or 11;
Q is CH2NHR6, CH2NO2, CH2N=CHR2, CH2N=C=O, CH2N+R3R4R5W-,
or (C=O)-R11;
X, Y, and Z are independently H or F, provided that at
least one of X and Y is F, and further provided that when Q is (C=O)-R11
each of X, Y, and Z is F;
W- is an agronomically acceptable anion;
R2 is an aromatic group;
each of R3, R4, and R5 is independently hydrogen; a lower
alkyl group, optionally substituted with at least one group selected from
hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxy-
carbonyl, and phenyl; one of R3, R4, and R5 is hydroxy and the other two
are hydrogen; or R3, R4, and R5 taken together with the nitrogen of Q
form a cyclic quaternary ammonium group;
R6 is hydrogen; an aliphatic group, optionally
substituted with at least one group selected from hydroxy, alkoxy, halo,
nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and phenyl; an
amino acid amide of Q;(C=O)-R7; C1-C12 aliphatic amines, optionally
substituted with at least one group selected from hydroxy, alkoxy, halo,

39
nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and phenyl; C2-
C12 aliphatic carboxylic acids, their esters, thiol esters, and amides, all
optionally substituted with at least one group selected from hydroxy,
alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and
phenyl; dihydro-3-oxo-pyrazolidinyl; or phenyl or thiophene, optionally
substituted with at least one group selected from hydroxy, alkoxy, halo,
nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and phenyl;
or R6 taken with the nitrogen of Q is guanidine;
hydrazine; alkyl or aryl hydrazine, optionally substituted with at least
one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol,
alkylthio, carboxyl, alkoxycarbonyl, and phenyl; or an alkyl or aryl
sulfonamide, optionally substituted with at least one group selected
from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl,
alkoxycarbonyl, and phenyl;
R7 is (C=O)-R14; C1-C12 aliphatic group optionally
substituted with at least one group selected from hydroxy, alkoxy, halo,
nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and phenyl; C2-
C12 aliphatic carboxylic acid, esters, thiol esters, or amides thereof, all
optionally substituted with at least one group selected from hydroxy,
alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl,
and phenyl; or a N, O, or S group such that when taken with the
carboxamide is a urea, semicarbazide, carbamate, or thiocarbamate
group, all optionally substituted with an alkyl or aryl group, optionally
substituted with at least one group selected from hydroxy, alkoxy, halo,
nitro, amino, thiol, alkylthio, carboxyl, alkoxy-carbonyl, and phenyl;
R11 is -OR12, -SR12, halogen, -NHOH, or -NR12R13;
each of R12 and R13 is independently hydrogen; an
aliphatic or an aromatic group, optionally substituted with at least one
group selected from hydroxy, alkoxy, halo, nitro, amino, thiol,
alkylthio, carboxyl, alkoxycarbonyl, and phenyl; a C1-C12 aliphatic

amine, optionally substituted with at least one group selected from
hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl,
alkoxycarbonyl, and phenyl; a C2-C12 aliphatic carboxylic acid, esters,
amides and salts thereof, optionally substituted with at least one group
selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio,
carboxyl, alkoxycarbonyl, and phenyl;
or R12 and R13 taken together with the N of R11 are a
protein amino acid or a cyclic group selected from morpholine,
piperidine, piperazine, or pyrrolidine, optionally substituted with at
least one group selected from hydroxy, alkoxy, halo, nitro, amino, thiol,
alkylthio, carboxyl, alkoxycarbonyl, and phenyl;
R14 is OH, alkoxy, NH2, or NHNH2;
or any agronomically acceptable salt thereof;
together with or in combination with
(a) formula II which is alkyl glycosides wherein the alkyl group is a
mixture of from about eight to about fourteen carbons and the number of
glycoside groups present in the formula are from one to about six;
(b) formula III which is a quaternized fatty amine ethoxylate wherein
the fatty amine is an alkylamine wherein the alkyl group is a mixture of
from about eight to about twenty carbon atoms, inclusive, and the
ethoxylate is an ethylene oxide monomer from about two to about fourteen
moles of ethoxylation;
(c) formula IV which is a mixture of (i) a fatty amine ethoxylate
wherein the fatty amine is an alkylamine wherein the alkyl group is a
mixture of from about six to about thirty carbon atoms, inclusive, and the
ethoxylate is an ethylene oxide monomer of from one to about fifty moles of
ethoxylation and (ii) ethoxylated alkylphenol wherein the alkyl is of from
zero to about twenty carbons, inclusive, the ethoxylate is an ethylene oxide
monomer of from about two to about twenty moles of ethoxylation;
(d) formula V which is ethoxylated acetylated diols wherein the
number of carbons in the acetylated chain is of from ten to twelve carbon

41
atoms, inclusive, and the ethoxylate is an ethylene oxide monomer of
from ten to about thirty moles of ethoxylation;
(e) formula VI which is a secondary alcohol or ethoxylate wherein
the ethoxylate is of from seven to fifteen, inclusive, of an ethylene oxide
monomer and the alkyl of the secondary alcohol or ethoxylate is of from
about seven to about fifteen, inclusive;
(f) formula VII which is an alkoxylated fatty amine oxide wherein
thealkyls are of from about six to thirty carbons, inclusive; and the
number of moles of alkoxylation are when taken together about from
one to fifty;
(g) formula VIII which is an alkyldimethyl amine oxide wherein
the alkyls are of from about six to thirty carbons;
(h) formula IX which is a fatty alcohol polyglycol ether wherein the
fatty alcohol represents a mixture of alkyls of from about six to thirty
carbons, inclusive; and the number of moles of ethoxylation are when
taken together about from one to fifty;
(i) formula X which is a coco esterified polyethoxyether wherein the
coco ester represents a mixture of alkyls of from about six to thirty
carbons, inclusive; and the ethoxylation is from one to fifty;
(j) formula XI which is a quaternary ammonium including an alkyl
of from C8 to C20 and an agronomically acceptable anion;
(k) formula XII which is a quaternary ammonium having groups
which are independently alkyl of from one to three carbons and
together are from two to seven carbons; and of from three to fifteen
ethylene oxide and propylene oxide groups and an agronomically
acceptable anion;
(1) formula XIII which is diamine ethoxylate with an alkyl of from
C8 to C20 and ethoxylation of from about from one to fifty;
(m) formula xrv which is an alkoxylated primary fatty alcohol with
an alkyl of from C13 to C18 and of from 6 to 50 propylene oxide groups;
and
(n) mixtures thereof.
2. A composition of claim 1 wherein the compound of the formula I is
an agronomically acceptable salt of 3,4,4-trifluoro-3-butene-1-amine, or

42
the monohydrochloride salt thereof; N-(3,4,4-trifluoro-3-butenyl)glycine
or the monohydrochloride salt thereof; 2-amino-N-(3,4,4-trifluoro-2-
butenyl)propanamide or the monohydrochloride salt thereof; (S)-2-
amino-4-(methylthio)-N-(3,4,4-trifluoro-3-butenyl)butanamide or the
monohydrochloride salt thereof; 4,4-difluoro-3-buten-1-amine or the
monohydrochloride salt thereof; 3,4,4-trifluoro-3-butenoic acid or the
sodium salt thereof; a combination of 3,4,4-trifluoro-3-butenoic acid and
3,4,4-trifluoro-3-buten-1-amine in a one to one ratio (1:); (S)-2-amino-3-
hydroxy-N-(3,4,4-trifluoro-3-butenyl)butanamide or the
mollohydrochloride salt thereof; N-(4,4-difluoro-3-butenyl)glycine,
methyl ester, or the monohydrochloride salt thereof; a combination of
3,4,4-trifluoro-2-butenoic acid and 2-propanamine in a one to one ratio
(1:1); N-(3,4,4-trifluoro-1-oxo-3-butenyl)glycine; 2-[(3,4,4-trifluoro-3-
butenyl)amino]acetamide or the monohydrochloride salt thereof; or
3,4,4-trifluoro-3-butenoic acid, 2-aminoethyl ester or the
monohydrochloride thereof.
3. A composition of Claim 1 wherein the adjuvant is
(a) the alkyl glycosides of the formula II wherein the alkyl group is
a mixture of from about nine to eleven carbons, inclusive, and the
number of glycoside groups present in the formula are from one to two;
(b) the quaternized fatty amine ethoxylate of the formula III
wherein the alkyl group of the fatty amine is a mixture of from eight to
sixteen carbon atoms and the number of moles of ethoxylates is two;
(c) the mixture of the formula IV is (i) the fatty amine ethoxylate of
the formula
<IMG>
wherein:

43
R22 represents a mixture of alkyls of from about twelve to twenty
carbons, inclusive; EO is an ethylene oxide monomer and n and m
represent the number of moles of ethoxylation in the formula and are
when taken together about from five to fifteen, and (ii) the ethoxylated
alkylphenol is the formula
<IMG>
wherein:
R23 is a mixture of alkyl groups of from about eight to ten carbons;
EO is the ethylene oxide monomer and w is the number of moles of
ethoxylation in the formula and is from about six to ten moles;
(d) the ethoxylated acetylated diols of the formula V is of formula
<IMG>
wherein:
* is a number of carbons to provide a total number of carbons in the
chain of from 10 through 12 carbons, inclusive; EO is ethylene oxide
monomer wherein q and p represent the number of moles of
ethoxylates in the formula and are when taken together 30;
(e) the secondary alcohol ethoxylate of the formula VI is
wherein:
<IMG>
R24a represents hydroxy or an ethylene oxide monomer wherein a
represents the number of moles of ethoxylate present in the formula

44
and is from nine to twelve, inclusive, and C* represents the ends of the
carbon chain such that altogether the chain is a mixture of carbons
having a total of from twelve to fourteen carbons, inclusive;
(f) formula VII which is an alkoxylated fatty amine oxide, preferably
Emcol XE 1656, including ethoxylated fatty amine oxide, preferably Flo-
Mo 3153 (the alkoxylated fatty amine oxide is represented by the
formula
<IMG>
wherein
R25 represents a mixture of alkyls of from about six to thirty
carbons, inclusive, preferably from about twelve to twenty carbons,
inclusive;
R' is hydrogen or methyl; and
z and z1 represent the number of moles of alkoxylation or preferably
ethoxylation in the formula and are when taken together about from
one to fifty, preferably five to fifteen);
(g) formula VIII which is an alkyldimethyl amine oxide, preferably
Empigen OB (the alkyldimethyl amine oxide may be represented by the
formula
<IMG>
wherein

R26 represents a mixture of alkyls of from about six to thirty
carbons, inclusive, preferably from about twelve to twenty carbons,
inclusive;
(h) formula IX which is a fatty alcohol polyglycol ether, preferably
Genapol T250 or Neodol (the fatty alcohol polyglycol ether may be
represented by the formula
<IMG>
wherein
R27 represents a mixture of alkyls of from about six to thirty carbons,
inclusive, preferably from about twelve to twenty carbons, inclusive; R'
is of hydrogen or alkyl of from one to two carbons;
Z2 represents the number of moles of ethoxylation in the formula
and are when taken together about from one to fifty, preferably five to
fifteen)
(i) formula X which is a fatty acid esterified polyethoxyether,
preferably Kaomul 230 or which is stearic acid polyethoxylate,
preferably Simusol M52( the coco esterfied polyethoxyether and stearic
acid polyethoxylate may be represented by the formula
R28-CO2-(EO)Z3-H
wherein
R28 represents a mixture of alkyls of from about twelve to twenty
carbons, inclusive;

46
EO represents ethoxylation in the formula and z3 is from five to
fifteen;
(j) formula XI which is a quaternary ammoniummay be
represented by the formula
R29?N+(CH3)2(CH2(C6H5)) Q-
wherein R29 represents alkyl from C10 to C16 and Q is an
agronomically acceptable anion;
(k) formula XII which is a quaternary ammonium represented by
the formula
R30R31R32N+(EO)n1(PO)n2 Q-
wherein R30, R31 and R32 are all methyl or one of R30, R31, R32 is
((EO)n1(PO)n2); EO is ethylene oxide; PO is propylene oxide; n1 is an
integer of one to two; and n2 is an integer of about six to ten; and Q is an
agronomically acceptable anion);
(l) formula XIII which is diamine ethoxylaterepresented by the
formula
<IMG>
wherein R33 represents alkyl of from about C10 to C16; and n3, n4, n5
represent the number of moles of ethoxylation in the formula and are
when taken together about from five to fifteen;
(m) formula XI which is an alkoxylated primary fatty alcohol,
represented by the formula
R?O(PO)n6(EO)n7

47
wherein R34 represents alkyl of from about C13 to C15; EO is ethylene
oxide; PO represents propylene oxide; n6 is an integer of from about 6 to
9; n7 is an integer from about 4.5 to 6;
and
(j) mixtures thereof.
4. A composition of Claim 2 wherein the formula is
(a) the alkyl glycosides which is APG 325 where the number of
glycoside groups is one to two and the alkyl group is a mixture of from
nine to eleven carbons;
(b) the quaternized fatty amine ethoxylate is cocomethyl ammonium
chloride or Ethoquad C/12;
(c) a mixture which is Improve?;
(e) the secondary alcohol ethoxylate is Tergitol 15-S-9, or Tergitol 15-
S-12; or
(f) mixtures thereof;
5. A composition of claim 4 wherein the adujuvant is the alkyl
glycosides of the formula II wherein the alkyl group is a mixture of
from about nine to eleven carbons, inclusive, and the number of
glycoside groups present in the formula are from one to two.
6. A composition of claim 5 wherein the formula I is N-(3,4,4-trifluoro-
3-butenyl)glycine or the monohydrochloride salt thereof.
7. A composition of claim 5 wherein the formula I is 3,4,4-trifluoro-3-
butene-1-amine, or the monohydrochloride salt thereof.
8. A composition for controlling nematode, insect, or acarid infestation
of a plant comprising an effective amount of a composition of Claim 1
in an agronomically acceptable carrier.
9. A composition for controlling nematode, insect, or acarid infestation
of a plant comprising an effective amount of a composition of claim 5 in
an agronomically acceptable carrier.
10. A composition for controlling nematode, insect, or acarid
infestation of a plant comprising an effective amount of a composition
of claim 6 in an agronomically acceptable carrier.

48
11. A composition for controlling nematode, insect, or acarid
infestation of a plant comprising an effective amount of a composition
of claim 7 in an agronomically acceptable carrier.
12. A method of controlling nematode, insect, or acarid infestation of a
plant, comprising applying to a plant locus an effective amount of a
composition of claim 1.
13. A method of systemically controlling nematode, insect or acarid
infestation of a plant, comprising applying to a plant locus an effective
amount of a composition of claim 9 that has or is transformed after
application to have polarity providing phloem mobility without
reducing nematode-controlling effectiveness.
14. A method of claim 12 wherein the compound of the formula I in the
composition is N-(3,4,4-trifluoro-3-butenyl)glycine or the
monohydrochloride salt thereof.
15. A method of claim 12 wherein the compound of the formula I in the
composition is 3,4,4-trifluoro-3-butene-1-amine, or the
monohydrochloride salt thereof.

Description

W095112977 ~1731~ PCT/US94/11731
ll~qPROVED coMPosmoNs FOR N~IATODE CONTROL
Field of the invention
The present invention relates to unexpectedly improved novel
compositions that cont~in a compound active on foliage in downward
5 systemic control of plant pests, ie parasitic nem~todes, insects and acarid
infestation. The composition is a compound, particularly as disclosed in
U.S. application Serial Number 07/827,231, filed February 3, 1992, which is
a continuation-in-part of U.S. Serial number 07/663,218, filed March 1,
1991, incorporated herein by reference therefor, and pllhli.shed in the
10 Patent Cooperation Treaty application Number PCT/US92/1474, in
comhin~t.ion v~ith an adjuvant selected from ~mong typical wetting,
dispersing or emulsifying agents used in agricultural formulations. The
invention relates also to a method for controlling nematodes, insects, and
acarids and to the use of the novel compositions.
Ba~k~round of the Invention
It is well-known to use wetting, dispersing or emulsifying agents
in fluorinated alkene-cont~ining neInAtocidal, insecticidal, or acaricidal
compositions. For ~ mple, the above noted U.S. application discloses use
of a blend of the calcium salt of dodecyibenzene sulfonate and nonionic 6-
20 molar ethylene oxide con-len~tion product of nonylph~nol, a blend of the
calcium salt of dodecylben~çne sulfonate and a nonionic 30-molar ethylene
oxide con(lçn~t.ion product of nonyl phenol, a nonionic paste of
polyalkylene glycol ether, refined xylene solvent and preferably Tween 20.
See also the above noted application, U.S. Patent 4,950,666, and
25 U.S. 4,876,285 for other typical surface-active wetting dispersing, and
emulsifying agents used in agricultural formulations. For ~mple, such
agents include the alkyl and alkylaryl sulfonates and sulfates and their
sodium salts; alkylamide sulfonates, including fatty methyltaurides;
alkylaryl polyether alcohols, sulfated higher alcohols, polyvinyl alcohols;

WO95/12977 ~ 1 7 3 1 ~ ~ - PCT/US94/11731
polyethylene oxides; sulfonated ~nim~l and vegetable oils; su fon~ted
petroleum oils; fatty acid esters of polyhydric Alcohol~ and the ethylene
oxide addition products of such esters; and the addition products of long-
chain mercaptans and ethylene oxide.
6 Additionally, U.S. Patent Nos. 5,237,100, 5,236,938, anl 5,232,949
disclose nematocides in compositions together with adjuvants including
synergists exemplified as piperonyl butoxide or ses~me~.
However, there reIn~in.~ a need in the art for nemato~ide,
insecticide, or acaridicide compositions having improved plant uptake,
10 systemic mobility, and desirably low effective levels of use.
~u~m~ry of the Invention
The present invention provides compositions for controlling
nematode, insect or acarid infestation of a plant, comprising a
quantitatively variable cornhin~tion of a compound of the formula I having
15 the structure
C - C~ ( CH2 ) n~ Q
Y Z
ao
wherein:
n=1,3,5,7,9,orll;
Q is CH2NHRg, CH2N02, CHzN=CHR2, CH2N=C=O, CH2N+R~4RsW-,
or (C=O)-Rll;
X, Y, and Z are independently H or F, provided that at
least one of X and Y is F, and further provided that when Q is
(C=O)-R11 each of X, Y, and Z is F;
W~ is an agronomically acceptable anion;
30 R2 is an aromatic group;

WO 95/12977 i~ 1 ~ 3 1 6 ~ PCT/US94/11731
each of R3, R4, and R~ is independently hydrogen; a lower
alkyl group, optionally substituted with at least one group
selected from hydloxy, alkoxy, halo, nitro, amino, thiol, alkylthio,
carboxyl, alkoxy-carbonyl, and phenyl; one of R3, R4, and Rs is
hyd~o~y and the other two are hydrogen; or R3, R4, and Rs taken
together with the nitrogen of Q form a cyclic quaternary
ammonium group;
R6 is hydrogen; an aliphatic group, optionally
substituted with at least one group selected from hydroxy, alkoxy,
halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and
phenyl; an amino acid amide of Q; tC=O)-R7; C1-C12 aliphatic
~mine~, optionally substituted with at least one group selected
from hyd,oxy, alkoxy, halo, nitro, amino, thiol, alkylthio,
carboxyl, alkoxycarbonyl, and phenyl; C2-(:~12 aliphatic carboxylic
acids, their esters, thiol esters, and amides, all optionally
substituted with at least one group selected from hydroxy, alkoxy,
halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and
phenyl; dihydro-3-oxo-pyrazolidinyl; or phenyl or thiophene,
optionally substituted with at least one group selected from
~0 hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl,
alkoxycarbonyl, and phenyl;
or R6 taken with the nitrogen of Q is gll~ni~line;
hydrazine; alkyl or aryl hydrazine, optionally substituted with at
least one group selected from hydroxy, alkoxy, halo, nitro, amino,
thiol, alkylthio, carboxyl, alkoxycarbonyl, and phenyl; or an alkyl
or aryl sulfonamide, optionally substituted with at least one
group selected from hydroxy, alkoxy, halo, nitro, amino, thiol,
alkylthio, carboxyl, alkoxycarbonyl, and phenyl;
R7 is (C=O)-R14; C1-C12 aliphatic group optionally

WO 95/12977 PCT/US94111731
~17~ 4
substituted with at least one group selected from hyd~ J~y, alkoxy,
halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and
phenyl; C2-C12 aliphatic carboxylic acid, esters, thiol ~sters, or
amides thereof, all optionally substituted with at least one group
selected from hyd~o~y, alkoxy, halo, nitro, amino, thiol, alkylthio,
carboxyl, alkoxycarbonyl, and phenyl; or a N, O, or S group such
that when taken with the carboxamide is a urea, sem~carbazide,
carbamate, or thiocarbamate group, all optionally sub-tituted
with an alkyl or aryl group, optionally substituted with at least
one group selected from hyd~oxy, alkoxy, halo, nitro, amino,
thiol, alkylthio, carboxyl, alkoxy-carbonyl, and phenyl
Rll is -ORl2, -SRl2, halogen, -NHOH, or-NR12R13 wherein
each of R12 and R13 is independently hydrogen; an
aliphatic or an aromatic group, optionally substituted with at
least one group selected from hydroxy, alkoxy, halo, n tro, amino,
thiol, alkylthio, carboxyl, alkoxycarbonyl, and phenyl; a Cl-C12
aliphatic amine, optionally substituted with at least ole group
selected from hydroxy, alkoxy, halo, nitro, amino, thiol, alkylthio,
carboxyl, alkoxycarbonyl, and phenyl; a C2-C12 aliphatic
~0 carboxylic acid, esters, amides and salts thereof, optionally
substituted with at least one group selected from hydlvl~y, alkoxy,
halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxyca1bonyl, and
phenyl;
or R12 and R13 taken together with the N of Rl1 are a
protein amino acid or a cyclic group selected from morpholine,
piperidine, piperazine, or pyrrolidine, optionally substituted with
at least one group selected from hydroxy, alkoxy, halo, Initro,
amino, thiol, alkylthio, carboxyl, alkoxycarbonyl, and phenyl;
R14 is OH, alkoxy, NH2, or NHNH2;
30 or any agronomically acceptable salt thereof;

~ WO 95/12977 ~ & ~ PC:T/US94J11731
together with or in combination with an activity enh~n~in~ amount of an
adjuvant of the
(a) formula II which is alkyl glycosides wherein the alkyl group
is a mixture of from about eight to fourteen carbons and the number of
5 glycoside groups present in the formula are from one to about six but
preferably one to two, and more preferably APG 325 or APG 225 where the
alkyl group is a mixture of from nine to eleven carbons or Atplus 258 or
either Rhodonat LMO which is coconut oil based sucroglyceride or
Rhodonat MLP 704 which is modified LMO sucroglyceride;
(b) formula III which is a quaternized fatty amine ethoxylate
wherein the fatty ~mine is an alkylamine wherein the alkyl group is a
mixture of from about eight to twenty carbon atoms, preferably a mixture
of from eight to sixteen carbon atoms, more preferably a mixture of from
eight to twelve carbon atoms such as is found in cocomethyl ~mmo~ium
15 chloride, and most preferably Ethoquad C/12 (the quaternized fatty amine
ethoxylate may be represented by the formula
(~O)xH
R20R2lN--(EO)yH z~
wherein:
R20 is a mixture of alkyl groups of from about eight to twenty-two
carbon atoms, inclusive;
R21 is an alkyl of from one to four carbons, inclus*e;
EO is an ethylene oxide monomer wherein x and y are
independently a number of from zero to fourteen and are the number of
moles of ethoxylation present with the proviso that x and y taken together
must be from two to fourteen, preferably two; and
Z- is an agronomically acceptable anion);

WO 95/12977 , P~T/US94/11731
~ ~ 7 ~ 6
(c) formula IV which is a mixture of a fatty amine ethoxylate
and ethoxylated alkylphenol, preferably Improve(~) (the fatty amine
ethoxylate may be represented by the formula
/ (EO)nH
R22N (EO)mH
wherein:
R22 represents a mixture of alkyls of from about six to thirty
carbons, inclusive, preferably from about twelve to twenty carbons,
inclusive,
EO is an ethyleneoxide monomer; and
n and m represent the number of moles of ethoxylation in the
15 formula and are when taken together about from one to fifty, preferably
five to fifteen, and the ethoxylated alkylphenol may be represented by the
formula
R23 ~--O(EO)wH
wherein:
R23 is a mixture of alkyl groups of from zero to twentyl carbons,
inclusive, preferably from about eight to ten carbons, inclusive, and more
preferably nine carbons;
EO is an ethylene oxide monomer; and
w is the number of moles of ethoxylation in the formula and is
from about two to twenty, inclusive, and preferably from six to ten moles,
inclusive);
(d) formula V which are ethoxylated acetylated diols, preferably
Surfynol 485, and more preferably present in the range from about 0.5%
(the ethoxylated acetylated diols may be represented by the formula

W095/12977 ~ ~L 7 3 i 6 ~ PCT/USg4/11731
CH3 CH3 CH3 CH3
,. I I I
C*, C--C~ C+C*
(EO)q O)P
wherein:
* is a number of carbons to provide a total number of carbons in
the chain of from 10 through 12 carbons, inclusive; and EO is an ethylene
oxide monomer wherein q and p indeper~ nt.ly are numbers which
represent the number of moles of ethylene oxide monomprs in the formula
and are when taken together in the range of from about 10 through 30,
15 inclusive, preferably 30);
(e) formula VI which is a secondary alcohol ethoxylate wherein
the number of moles of ethylene oxide monomers is from 7 to 15, inclusive,
preferably Tergitol(~) 15-S-7, Tergitol(g) 15-S-9, or Tergitol~) 15-S-12, and
more preferably Tergitol~g) 15-S 12 (the formula VI may be shown as
ao follows:
~CH R24a CH3 fH3
\CH2/ \CH2~ ~CH2
wherein:
R24a represents hydloky or a Polyoxyethylene group wherein a
represents the number of moles of ethylene oxide mo~omers present in
- the formula and is from about seven to fifteen, inclusive, preferably about
30 nine to twelve, inclusive, and C* represents the ends of the carbon chain
such that altogether the chain is a mixture of carbons having a total of

wo 95/12977 PCT/US94/11731
~731~ 8
from eleven to fifteen carbons, inclusive, preferably from twelv~ to
fourteen carbons, inclusive);
(f) formula VII which is an alkoxylated fatty amine oxide,
preferably Emcol XE 1656, including ethoxylated fatty amine oxide,
5 preferably Flo-Mo 3153 (the alkoxylated fatty amine oxide is represented by
the formula
O ~
R2s N (CHCH20
(CHCH20)z H
~' .
15 wherein
R2s represents a mixture of alkyls of from about six tolthirty
carbons, inclusive, preferably from about twelve to twenty carbons,
inclusive;
R' is hydrogen or methyl; and
~ao z and z1 represent the number of moles of alkoxylation or
preferably ethoxylation in the formula and are when taken together about
from one to fifty, preferably five to fifteen);
(g) formula VIII which is an alkyldimethyl amine oxide,
preferably Empigen OB (the alkyldimethyl amine oxide may be
25 represented by the formula

WO 9S/12977 ~ ~ 7 31 6 ~ PCTIUS94/11731
R26 N CH3
CH3
whereln
R26 represents a n~i~lu~ e of alkyls of from about six to thirty
carbons, inclusive, preferably from about twelve to twenty carbons,
10 inclusive;
(h) formula IX which is a fatty alcohol polyglycol ether,
preferably Genapol T260 or Neodol (the fatty alcohol polyglycol ether
may be represented by the formula
~'
~5
R2~ O(CHCH2)z2--OH
wherein
R27 represents a mixture of alkyls of from about six to thirty
20 carbons, inclusive, preferably from about twelve to twenty carbons,
inclusive; R' represents alkyl of from about one to two carbons,
inclusive;
Z2 represents the number of moles of ethoxylation in the
formula and are when taken together about from one to fifty, preferably
25 five to fifteen)
(i) for~nula X which is a fatty acid esterified polyethoxyether,
preferably Kaomul 230 or which is stearic acid polyethoxylate,
preferably Simusol M62( the coco esterfied polyethoxyether and stearic
acid polyethoxylate may be represented by the formula

WO 95/12977 PCT/US94tll731
R28 C02--(E0~3 H
wherein
R2g represents a ~ ll e of alkyls of from about six to thirty
5 carbons, inclusive, preferably from about twelve to twenty c~rbons,
inclusive;
EO represents ethoxylation in the formula and Z3 iS from one
to fifty, preferably five to fifteen);
or
(j) formula XI which is a quaternary ammonium, preferably
Dodigen 226 (the quaternary ammonium may be represented by the
formula
R29--N (CH3)2(CH2(C6Hs)) Q
wherein R2g represents alkyl from C8 to C20, preferably C10 to C16 and
1~ Q is an agronomically acceptable anion);
(k) formula XII which is a quaternary ammoniuIr,
preferably Dodigen 4022 (the quaternary ~mmonium may b~
represented by the formula
R3oR3lR32N (E)nl(Po)n2 Q
wherein R30, R31 and R32 are independently alkyls of from one to three
carbons which together are from two to seven carbons, preferably all
methyl, or one of R30, R31, R32 is ((EO)n1(PO)n2); EO is ethylene oxide;
PO is propylene oxide; nl is an integer of one to two; and n2 - s an
25 integer of three to fifteen, preferably six to ten; and Q is an
agronomically acceptable anion);
(1) formula XIII which is ~ mine ethoxylate, preferably
Ethoduomeen (the (li,qmine ethoxylate may be represented by the
formula
R33\ ~EO)nS
(EO)n3 (~)n4
,

WO 95/12977 PCT/US94/11731
7~16~
wherein R33 represents alkyl of from C8 to C20, preferably C10 to C16;
and n3, n4, ns represent the number of moles of ethoxylation in the
formula and are when taken together about from one to fifty, preferably
five to fi~Geen);
(m) formula XIV which is an alkoxylated primary fatty
s~lçohnl, l,refelably Ethylan CPG 945 (the alkoxylated primary fatty
alcohol may be represented by the formula
R34 (PO)I~ (EO~
10 wherein R34 represents alkyl of from C8 to C18, preferably C13 to C15;
EO is ethylene oxide; PO represents propylene oxide; n6 is an integer of
from 6 to 50, preferably from 6 to 9; n7 is an integer from 4 to 8,
preferably 4.5 to 6;
and
(n) mixtures thereof.
Most preferably the adjuvant is of the formula represented by
Improve(~) or Tergitol(~) 15-S-12.
More preferably the compound of the formula I is an
agronomic~lly acceptable salt of 3,4,4-trifluoro-3-butene-1-amine,
20 preferably the monohydrochloride salt thereof; N-(3,4,4-trifluoro-3-
butenyl)glycine, preferably the monohydrochloride salt thereof; 2-
amino-N-(3,4,4-trifluoro-2-butenyl)propanamide, preferably the
mnonohydrochloride salt thereof; (S)-2-amino-4-(methylthio)-N-(3,4,4-
trifluoro-3-butenyl)but~n~mide, preferably the monohydrochloride salt
2B thereof; 4,4-difluoro-3-buten-1-amine, preferably the
monohydrochloride salt thereof; 3,4,4-trifluoro-3-butenoic acid,
preferably the sodium salt thereof; a combin~t.ion of 3,4,4-trifluoro-3-
butenoic acid and 3,4,4-trifluoro 3-buten-1-amine in a one to one ratio
(1:); (s)-2-amino-3-hydroxy-N-(3~4~4-trifluoro-3-butenyl)but~n~mide~
30 preferably the monohydrochloride salt thereof; N-(4,4-difluoro-3-
butenyl)glycine, methyl ester, preferably the monohydrochloride salt
thereof; a co-mhin~tion of 3,4,4-trifluoro-2-butenoic acid and 2-
prop~n~mine in a one to one ratio (1:1); N-(3,4,4-trifluoro-1-oxo-3-

PCT/US94/11731
butenyl)glycine; 2-[(3,4,4-trifluoro-3-butenyl)amino]acetamide,
preferably the monohydrochloride salt thereof; or 3,4,4-trifluoro-3-
butenoic acid, 2-aminoethyl ester, preferably the mo~ohydrochloride
thereof.
More preferably the parasitically active ingredient is 3,4,4-
trifluoro-3-butene-1-amine, preferably the monohydrochloride salt
thereof; or N-(3,4,4-trifluoro-1-oxo-3-butenyl)glycine and mo -t
preferably the active ingredient is N-(3,4,4-trifluoro-1-oxo-3-
butenyl)glycine.
It is surprising that a comhin~*on of a compound of the
formula I and from about 0.05 to 20 % but less than an amount toxic to
an infested plant, preferably about 0.10 to 2 %, of an adjuvant active
ingredient of the formula II, III, IV, V, VI or mixtures therleof
increases the effectiveness of the compound of formula I against
15 parasitic, particularly nematode infestation when applied to foliage of
the infested plants by an unexpected difference compared to -,he a
combination of the compound of formula I with other known surface-
active wetting dispersing, and emulsifying agents commonly used in
agricultural formulations. An ordinarily skilled artisan would be able
ao to find the % of adjuvant effective for a particular compound of the
formula. The percentage expressed is by volume.
Therefore, the present invention is also a method fo-
controlling nematodes, insects, and acarids and for the use of the novel
compositions for controlling nematodes, insects, and acarid-
25 comprising treating an infestation of nematodes, insects, and acaridseither on the foliage or the soil of infested plants with a compound of
the formula I together with an activity enhancing amount of an
adjuvant of the formula II which is alkyl glycoside, preferabiy APG~
325 or Atplus 258 in the amount of 0.25-1%;
30 an adjuvant of the formula III which is ethoxylated cocomethyl
ammonium chloride, preferably Ethoquad C/12 in the amount of 0.25-
1~; .
an adjuvant of the formula IV which is fatty amine ethoxylate,
preferably Improve(g in the amount of 0.25-2%;

WO 9S/12977 ~ 1 7 3 1 li ~ PCI/US94/11731
~3
an adjuvant of the formula V acetylenic diol ethoxylate, preferably
Surfynol 485 and preferably in the amount of 0.5-1%; or
an adjuva~lt of the formula VI an ethoxylated seco~ ry ~lcohol~
~ efe~ably Tergitol(~ 15-S-7 in the amount of about 0.5%, Tergitol(~) 15-
5 S-9 in the amount of about 0.5~o, or Tergitol~) 15-S-12 in the amount of
0.5%.
Detailed Descri~tion of the Invention
The novel compositions of the present invention are useful as
an unexpectedly effective systemic composition for controlling
10 nematode, insect, and acarid infestation of a plant. These
compositions provide a lower effective foliar use rate of compound of
formula I while m~int~inin~ efficacy in nematode, insect, and acarid
disease control. That is, when applied to the foliage or stems of a plant
they are able to move through the phloem and xylem of the plant and
15 provide control of nematodes, insects, or acarids at other locations of
the plant.
The present methods for systemic control of nematodes,
insects, and acarids use unexpectedly enhanced phloem mobile
compositions of the present invention. These compositions having a
20 compound of Formula I and a sufficient amount of an adjuvant to
unexpectedly provide enh~nced effectiveness. It has been proposed the
enh~nced effectiveness of the present compositions results from
improved phloem mobility in order to relocate the compound of
Formula I downward in a plant without elimin~ting the nem~tode-,
25 insect- or acarid-controlling activity of the compound of Formula I.
To effectively control nematodes or other pests systemically by
application to the above-ground surfaces of a plant, the present
compositions may improve the active ingredient capability of passing
through the cuticle of the foliage or stem of a plant, passing into the
30 phloem, and rem~ining there long enough to be transported
throughout the plant so as to move to untreated areas including theroots. There such a compound of formula I may leak out or in some
way contact the pests to such an extent that they are killed or repelled
and the rl~m~ge they would do to the plant is reduced or elirnin~ted.

WO 95/12977 PCT/US94/11731
s~ 3 1 6 ~ I
14
,
During these steps throughout the plant, a compound of formula I may
undergo ~hemic~l reactions, such as hydrolysis, or biologic~l
reactions, such as enzymatic actions. In addition, the form~lla I of the
present invention may be devised which, when placed on th~ plant,
5 prior to absorption into the plant, may undergo reactions thfit result in
a compound that is readily absorbable, translocatable, and effective in
~l~v~nting pest l~m~ge. An example of such compounds a-e those
having W-labile protecting groups which when exposed to natural
light undergo reaction and result in active and mobile derivatives of
10 compounds of the formula I. Another example is silylated amine
derivatives.
Therefore, what is placed on the foliage or stem of tne plant
may not be a composition wherein the compound of formula I is
~ctll~lly transported or the compound of formula I that actu lly
~5 controls the pest. Thus, the methods of the present inver tion
provide for compositions that may be transformed through chemical or
biological reactions to have proper polarity for systemic activity.
Although the methods of the present invention include
applying composition to the plant locus, preferably to the fol age, are
20 known, the present compositions are surprising combinations of
compounds of the formula I as defined above and selected adjuvants of
the formulae II, III, IV, V, VI or mixtures thereof. These
combinations are for adjuvants that can not be predicted from among
those commonly used in agronomics.
26 Among the compounds of the formula I, in order to control
nematodes it is preferred that n is 1 and X, Y,
and Z are all F, and Q1 is then CH2NH3+W-, that is, a salt of
3,4,4-trifluoro-3-butene-1-amine. VVhen Q1 is CHzNHR6, R6 is
preferably an alpha-amino acid linked by a peptide (amide) bond, more
30 preferably a protein amino acid. When Q1 is (C=O)-Rll, Rll is
preferably hydlol~yl and the compound is thus 3,4,4-trifluoro~-3-butenoic
acid or a salt thereof, including a salt formed with

WO 95112977 ~ 1 7 ~ 1 6 ~ PCT/US94~1 I 731
,5
3,4,4-trifluoro-3-butene-1-amine, that is,
3,4,4-trifluoro-3-butene-1-amine 3,4,4-
trifluoro-3-buten o~te
W- may be any agronomically acceptable anion.
5 This includes, but is not limited to chloride, iodide,
bromide, oxalate, sulfate, phosphate, citrate, acetate,
or a fluoro~lkene carboxylate, for qx~mple,
F2C=CFCH2COO-.
In addition to the compounds specifically
10 described above, all agronomically acceptable salts of
the compounds are within the scope of the present
invention. For example, a compound of the present
invention having a free amine group may also exist as
the protonated form having various anions associated
15 therewith, for example, but not limited to, chloride, bromide, iodide,
phosphate, o~ te, sulfate, citrate,and acetate. In addition, a
fluoroalkene carboxylate ion, such as F2C=CFCH2COO-, may be the
counter-ion.
A compound of the present invention having a carboxylic
20 acid or hydroxyl group may exist as the salt having
various cations associated therewith, for e~mple, but
not limited to, alkali earth metals, such as sodium,
calcium, and potassium; magnesium; or quaternary
ammonium ions, such as ammonium, mono-, di-, or
25 trialkylammonium, for ç~r~mple, isopropyl~mmonium, or
pyridinium. In addition, a fluoro~lkerlyl ammonium ion,
such as F2C=CFCH2CH2NH3+, may be the cation. All such
compounds and others having simil~qr characteristics,
being agronomically acceptable, are encomp~sed by the present
30 invention.
As used herein, the term "halo", "halide", or "halogen"
mP~n~ fluorine, chlorine, iodine, or bromine or cogn~tes thereof.
The term "alkyl" in the definitions of the formula I means
straight-chain or branched groups of from one to about seven carbon

WO 95tl2~77 i~ PCT/US94/11731
16
atoms. The term "lower alkyl" me~n~ a such a group cont~ ning from
one to about four carbon atoms. The term "aliphatic" mean saturated
or unsaturated, branched or straight-chain, alkyl groups h~ving from
one to ten carbon atoms. I
The term "alkoxy" means a lower alkyl group bonded via an
oxygen atom. The term "alkylthio" me~n~ a lower alkyl group bonded
via a sulfur atom. The term "alkoxycarbonyl" means the lowl er alkyl
ester of a carboxyl group. I
The term "aliphatic amine" means an aliphatic group
1~ wherein at least one hydrogen is replaced with -NH2. The term
"aliphatic carboxylic acid, its esters, thiol esters, and amide-" means
an aliphatic group wherein at least one carbon is a carboxylic group,
-COOH, or is the lower alkyl ester, lower alkyl thiol ester, or amide
thereof.
~5 The term "aromatic group" or "aryl" means phenyl.
optionally substituted with at least one group selected from hydroxy,
alkoxy, halo, nitro, amino, thiol, alkylthio, carboxyl, alkoxycarbonyl,
and phenyl. It should be obvious to one of ordinary skill in th.~ art that
heterocycles could also be used for the aromatic group, for example,
20 t~ 7ole, pyridine, thi~ole, isothi~ole, oxazole, pyrazole, triazole,
benzothiazole, thiophene, furan, and the like, all of which may also be
optionally substituted.
As used herein, the phrase "amino acid amide of Q" (or Q1)
means that R6 is an amino acid coupled via a peptide (amide) bond to
25 the N of CH2NHR6. This amino acid may be a natural, i.e., protein,
amino acid or a nonnaturally occurring amino acid. The amino group
of the amino acid may be a substituent of any carbon in the g loup, for
example, alpha, beta, or gamma to the carbonyl.
The term "alkyl or aryl hydrazine" means a hydrazine group
30 substituted with a lower alkyl or phenyl group, which in turn may be
optionally substituted. The term "alkyl or aryl sulfo~mi~e" means a
sulfonamide group substituted with a lower alkyl or phenyl g~oup,
which in turn may be optionally substituted.

WO 95/12977 ~ ~ 7 3 ~ ~ ~ PCT~US94/11731
17
COMPOUND SYNTHESIS
Methods of preparation for the compounds of formula I of the
present invention are described in PCT application Number
PC:~T/US92/1474 which is incorporated by reference therefor.
FORMULATIONS
In normal use, the compositions usually will not be employed
free from further admixture or dilution, but ordinarily will be used in a
suitable formulated composition comp~t.ible with the method of
application and comprising an effective amount of the composition.
10 The compositions of this invention may be blended with additional
agriculturally acceptable surface-active agents and carriers normally
employed for facilitating the dispersion of active ingredients,
reco~ni7.ing the accepted fact that the formulation and mode of
application may affect the activity of the composition. The present
15 composition may be applied, for example, as sprays, dusts, or
granules, to the area where pest control is desired, the type of
application varying with the pest and the environment. Thus, the
compositions of this invention may be formulated as granules of large
particle size, as powdery dusts, as wettable powders, as em~ ifi~ble
20 concentrates, as solution, and the like.
Granules may comprise porous or nonporous particles, such
as attapulgite clay or sand, for e~mple, which serve as carriers for
the present compounds. The granule particles are relatively large, a
diameter of about 400-2500 microns typically. The particles are either
25 impre~n~te~l with the composition of the invention from solution or
coated with the composition, ~lhesive sometimes being employed.
Granules generally contain 0.05-10%, preferably 0.5-5%, active
ingredient.
Dusts are admixtures of the compounds, with finely divided
30 solids such as talc, attapulgite clay, kieselguhr, pyrophyllite, chalk,
diatomaceous earths, calcium phosphates, calcium and magnesium
carbonates, sulfur, flours, and other organic and inorganic solids
which act as carriers for the compound. These finely divided solids

wo 95/12977 ~ ~3L 7 3 1 G ~ rcTlusg4/ll73l
18 '
have an average particle size of less than about 50 microns. A typical
dust formulation cont~in~ 1 part of compound and 99 parts o ~ talc.
The compositions of the present invention may be m de into
liquid concentrates by dissolution or em~ ification in suitab' e liquids
5 and into solid concentrates by ~lmi~tllre with talc, clays, and other
known solid carriers used in the agricultural chemical art. The
concentrates are compositions cont~ining about 5-50~o active
composition'of which 98.00-99.25% may be of the formula I and 0.25- 2%
may be adjuvant and 95-50% inert material, which includes surface-
10 active dispersing, emulsifying, and wetting agents not withir thedefinition of adjuvant herein, but even higher concentrations of
pesticidal active ingredient or adjuvant active ingrec'ient may
be employed experiment~lly. The concentrates are diluted with water
or other liquids for practical application as sprays, or with acditional
15 solid carrier for use as dusts.
A typical 50% wettable powder formulation would consist o
50.0% (wt/wt) of the composition, 22.0% attapulgite diluent, 2~ .0% of
kaolin diluent, and 6.0% sodium salts of sulfonated Kraft lignin
emulsifier.
~0 Typical carriers for solid concentrates (also called wPttable
powders) include fuller's earth, clays, silicas, and other high:y
absorbent, readily wetted inorganic diluents. A suitable solid
concentrate formulation may contain 1.5 parts each of sodium
lignosulfonate and sodium lauryl sulfate as additional wettin agents,
25 25 parts of active compound and 72 parts of attapulgite clay. I
Manufacturing concentrates are useful for shipping low
melting products of this invention. Such concentrates are prepared by
melting the low melting solid products together with one percent or
more of a solvent to produce a concentrate which does not solidify on
30 cooling to the freezing point of the pure product or below.
Useful liquid concentrates include the emlll.cifi~hle
concentrates, which are homogeneous liquid or paste compos'tions
readily dispersed in water or other liquid carriers. They maylconsist
entirely of the active compound with a liquid or solid emulsifying

WO 9~/12977 21 7 ~ PCT/US94111731
19
agent, or they may also contain a liquid carrier such as xylene, heavy
aromatic naphthas, isophorone and other relatively non-volatile
organic solvents. For application, these concentrates are dispersed in
water or other liquid carriers and normally applied as sprays to areas
5 to be treated.
A typical 50 gram per liter çm~ ifi~hle concentrate
formulation would consist of 5.9% (wt/wt) of a composition of the
invention; as emulsifiers a 1.80% of a blend of the calcium salt of
dodecylbenzene sulfonate and nonionic 6-molar ethylene oxide
10 contlen~tion product of nonylphenol, 2.70~o of a blend of the calcium
salt of dodecylbenzene sulfonate and a nonionic 30-molar ethylene
oxide condensation product of nonylphenol, 1.50% of a nonionic paste of
polyalkylene glycol ether, and 88.10% refined xylene solvent.
Typical surface-active wetting, dispersing, and emulsifying
16 agents for use in formulations in addition to the adjuvants of the
present invention are other agricultural formulations which include,
for example" the alkyl and alkylaryl sulfonates and s~llf~qte~ and their
sodium salts; alkylamide sulfonates, including fatty methyl taurides;
alkylaryl polyether alcohols, sulfated higher alcohols, polyvinyl
20 alcohols; polyethylene oxides; sulfonated ~nim~l and vegetable oils;
sulfonated petroleum oils; fatty acid esters of polyhydric alcohols and
the ethylene oxide addition products of such esters; and the addition
products of long-chain mercaptans and ethylene oxide. The surface
active agent normally comprises about 1-16% by weight of the active
25 ingredient. Thus, in the present compositions the surface active agent
in addition to the adjuvant of the present invention composition may
reduce this percentage of other surface active agents used to formulate
this composition.
Other useful formulations include simple solutions of the
30 invention composition in a solvent in which it is completely soluble at
the desired concentration, such as water, acetone, or other organic
solvents. The preferred formulation for foliar applic~tion is an
aqueous solution, more preferably cont~ining a sufficient amount of
adjuvant to provide an enh~nced parasitically active compound of the

W09S112977 r¦3~6~ PCT/US94/11731 !--
ZO
formula I as well as provide the desired concentration. However,
glycerin and other surface active agents such as Tween(~)20, and most
preferably 1% glycerin and 0.1% Tween(~)20 may also be part of the
formulation.
The compositions may be formulated and applied with
suitable pesticidal active ingredients, including insecticides,
acaricides, fungicides, plant regulators, herbicides, fertilizers, etc.
~,THOI:)S OF U~
The present invention provides methods of controlling various
10 pests that prey on agricultural crops, namely nematodes, in ects, and
acarids. An infestation of a plant by any of these pests may be
controlled by applying to the plant locus an effective amount of any of
the compounds of the present invention. The application may be made
in a variety of ways, including applying the compound or a composition
1~ cont~ining it to the soil before or after pl~qntinE or emergence, to the
seed or seed pieces prior to or at pl~nting, and to the plant fo:iage,
stems, or trunks. The tre~tment may be made more than oLce during
a growing season with one or more days between treatments~ An
appropriate treatment schedule will depend on the life cycle of the pest
20 to be controlled, ambient temperatures, and moisture levels. In
addition the age or size of the plant may influence the tre~tn ent
schedule. I
The methods of the present invention may be carried out on a
variety of crops. These include, but are not limited to, fruit and
25 vegetable crops, such as potatoes, sweet potatoes, carrots, tomatoes,
grapes, peaches, citrus, b~n~n~, corn, and soybeans; tobacco; and
cotton.
(:~ompounds of the present invention may be used to 7Ontrol
any of the phytopathogenic nematodes. Insects which may b~
30 controlled by the methods of the present invention include, but are not
limited to, foliar pests such as green peach aphids, and soil-borne pests
such as southern corn rootworm. Acarids which may be con-,rolled by
the methods of the present invention include, but are not limi ,ed to two
spotted spider mites. Although no tests have been specifically

WO 95112977 ,~ PCT/US94/11731
21
performed using the compositions tests conducted with a few of the
parasitically active compounds of the present invention revealed no
significant level of control of tobacco budwo~ or Colorado potato
beet~le.
A preferred rate of application of a composition wherein the
compound of the formula I is enh~nced by coml~in~tion with from
0.25% to 2~o by weight of active adjuvant of the formula II, for ex~mple
in comhin~tion is found to be about 4 or 8 oz/acre to obtain levels of
control (80-100%) that are comparable at 16 oz/acre with Triton CS7 for
10 control of root knot nçm~todes.
TEST EXAMPLES
The following methods were used to evaluate adjuvants that
are combined with a compound of formula I, specifically, for example,
N-(3,4,4-trifluoro-1-oxo-3-butenyl)glycine.
A track sprayer is used for foliar applications to appro~im~te
application procedures and volumes commonly used in the field ( 25
gal/A). Twenty mls of each test solution is formulated in water,
estimating that 10 mls would ~ctll~qlly be applied to the 5
plants/treatment (5" or 6" round pots; soil mix: 50% Metromix, 26%
~) fine sand, 25~o medium sand, with 136 g Osmocote 14-14-14m3; one 3-4
week old Rutger tomato plant/pot). Plants are often transplanted into
the 5" or 6" pots; at least one day is allowed between transplanting and
treAtmçnt. Pots are spaced along the track sprayer's 5 ft long center
strip. A single 8001E nozzle tip is placed in a boom directly over the
25 plants and adjusted to 6-9" above the leaf canopy. Pressure is set to
15psi, resulting in 4.2-4.5 ml/sec release. The track sprayer speed is
adjusted to approximately 95 on the dial giving an LCD speed readout
of 1.75-1.85. Generally, tests are comprised of 20 treatments plus an
- uninoculated control tre~tmçnt.
After chemical application, plants are allowed to dry for 2-4
hours and are then inoc~ tefl.
4-6 shallow holes are made in proximity to the plant stem using a thick
pen, for the addition of Meloidogyne incognita (root knot) nçm~tode
eggs. 30 mls of egg suspension (720 eggs/ml, 21,000 eggs/plant) are

WO 95/12977 . PCT/US94/11731
~17~16~
distributed among all holes in a pot using a large syringe. Plants are
ran-lomi~ed before inoculation and then moved to either Greelnhouse 16
or 21 for 3-4 weeks incubation. Greenhouse day temperatures are 25-30
C and supplemental overhead light brought day length to 12 hours. At
5 evaluation, foliage is ~mined for phytotoxic effects and ther stems
are cut to 1-2 inches above soil level. ~reS~ soil is ~h~qken frorl root ball
and roots are washed free of soil mix using a high pressure ~ater
nozzle. Roots are evaluated for severity and quantity of f~llin~ visible
and each replicate given a disease severity rating 0-100%. Thi - data is
10 entered into a SAS program and results are compared to both the
inoculated control and (S)-2-amino-4-(methylthio)-N-(3,4,4-trifluoro-3-
butenyl)but~n~mide, monohydrochloride, with Triton CS7 or (S)-2-
amino-4-(methylthio)-N-(3,4,4-trifluoro-3-butenyl)but~n~mide,
monohydrochloride, without adjuvant. Several commercial and
1~ experimental adjuvants were tested and are listed below with their
active ingredient and percentages identified as follows:
TABLE 1
Adjuvant %ai Active Ingredient
NH3S04 100 ammonium sulfate
APG~ 225 70 alkyl glycoside
APG~ 300 50 alkyl glycoside
APG~ 32~ 70 alkyl glycoside
Arquad T 127W 27 trimethyl tallow ammonium
chloride
Buffercide 10 phosphoric acid
2~ Cayuse 42.5 phosphate ester of
polyg Iycoethers
+ 16.5 ammonium salts
Improve~ 64 fatty amine ethoxylate
+ 14 ethoxylated nonylphenol

WO 95112977 PCTIUS94/11731
CropOil 17 polyoxyethylated polyol fatty
acid ester + polyol fatty acid
ester
Ethoquad C/2~ 100 cocomethyl 15EO ammonium
chloride
Ethoquad C/12 100 cocomethyl 2EO ammonium
chloride
Emcol~ CC9 100 propoxylated quaternary amine
5 Glycerin 100 glycerin
MON 0818 15 polyoxyethylene alkyl (tallow)
amine
Nitrogen 2 8 28% nitrogen
nonylphenol 4EO 1 0 0 nonylphenol 4EO
nonylphenol 6EO 100 nonylphenol 6EO
nonylphenol 8EO 100 nonylphenol 8EO
nonylphenol 10EO 100 nonylphenol 10EO
nonylphenol 12EO 100 nonylphenol 12EO
R- 11 9 0 octyl phenoxy ethanol
Silwet L77 100 organosilicone ethoxylate
Surfynol 465 100 10 mole EO acetylenic diol
ethoxylate
Surfynol 48~ 100 30 mole EO acetylenic diol
ethoxylate
Tergitol~ 15-S-3 100 C11-C1s secondary alcohol EO
Tergitol~ 15-S-5 100 C11-C1s secondary alcohol EO
Tergitol~ 15-S-7 100 C11-C15 secondary alcohol EO
Tergitol~ 15-S-9 100 C11-C1s secondary alcohol EO

WO 95/12977 217 3 1 ~ ~ 24 PCT/US94/11731
Tergitol~ 15-S-12 100 C11-C1s secondary alc~hol EO
Tergitol~ 15-S-15 100 C11-C1s secondary alc~hol EO
Tween 20 10 0 polyoxyethylene (20) sorbitan
monolaurate
Triton~ CS-7 6 0 alkyl aryl polyethoxylate and
sodium salt of alkyl sl Ifonated
alkylate
5 Varion CDG-K 28 lauryl betaine
The following results using the above methods show compounds
of the formula I, ie 2-amino-N-(3,4,4-trifluoro-2-butenyl)proFanamide,
monohydrochloride salt (denoted as A hereinafter), (S)-2-am no-4-
10 (methylthio)-N-(3,4,4-trifluoro-3-butenyl)bllt~n~qmi~le,
monohydrochloride salt (denoted as B hereinafter), 3,4,4-trifluoro-3-
butenoic acid, sodium salt (denoted as C hereinafter), N-(3,4,4-
trifluoro-1-oxo-3-butenyl)glycine(denoted as D hereinafter), 2- (3,4,4-
trifluoro-3-butenyl)amino]acetamide, monohydrochloride sal, (denoted
~5 as E hereinafter), 3,4,4-trifluoro-3-butenoic acid, 2-aminoethyll ester,
monohydrochloride salt (denoted as F hereinafter), thereof that the
selected adjuvants of the present invention combination provide an
unexpected enhancement of the compound of the formula I. (~FOR I)

WO 9~i/12977 ~; . PCT/US94/11731
7 ~ i 6~ ~
TABLE 2
cont'd
- FOR l* Ad juvant Adj% 16 8 4 2
B no ad 3~ 38
5 B no ad ~' 1';
B no ad 28 1'
B no ad 35 22
B no ad 38 24
B no ad 24 9
B no ad 19 6
B NH3S04 2 2 2 9
B APG~ 225 .25 59 14
B APG~ 225 .25(ai) 47 9
B APG~ 225 .5 ~2 36
~5 B APG~ 225 1 ,6 34
B APG~225 1(ai) 88 '9
B APG~ 300 .25 37 16
B APG~ 300 .25(ai) 58 7
B APG~ ' 00 .5 73 19
ao B APG~ 3~00 1 67 40
B APG~ 300 1(ai) 92 55
B APG~ 325 .25 88 49
B APG~ 325 .25(ai) 64 9
B APG~ 32. .5 74 6 9
B APG~ 32, 1 70 29
B APG~ 325 1(ai) 96 47
B Arquad T .25(ai) 31 2
B Buffercide .25 12 8
B Cayuse .25 41 21
3 Cayuse .75 47 27
3 CropOil .5 43 18
3 CropOil 2 3 0 2 5
B CS7 .5 28 7
B CS7 .5 98 33 3
36 B CS7 .5 81 28 3
B CS7 .5 81 24 1
B CS7 .5 92 62 21
B CS7 .5 51 18 9

WO 95/12977 ~ 17 316 ~ 1CT/US94/11731
æ
.. . . .
B CS7 .5~ai) 95 58 21
B C'`7 .5(ai) 93 63 54
B CS7 .5(ai) 100 8 1 2 1
B CS7 .5(a) ,n 11
5 B CS7 .5(a )
B CS7 .5(a ) , , '~
B CS7+NH3SO4 .5+2 2 3 14
B CS7+28%N . 5+2 17 8
B CS7 .5 9 0 4 l)
B Emco~ CC9 1 5 51
B Emco~ CC9 5 18 5
B Ethoquad C/12 .25 91
B Ethoquad C/12 .25(ai) 67 1 ç
B Etloquad C/12 .5 91
B Etloquad C/12 1 98
B Ethoquad C/12 1 (ai) 79 50 B
B Ethoquad C/25 1 21 8
3 Ethoquad C/25 5 38p 2
3 Ethoquad C/25 2.5(ai) 3 6
3 E 1oquad C/25
+Surfynol 465 .5(ai) 62 2r,
C Gycerin 1(a) 82 4
D Glycerin 1 (a ) 61 27
B Improve~ .25 7 3 10
B Improve~ .25 100 7' 1 5
B Improve~ .5 80 2'
B Improve~ .5 9 3 30
B Improve~ .5 100 98 28
B Improve(~ '(a ) 94 51-
30 B Improve~ ~(a ) 9 6 62
B Improve~ .5(ai) 93 3
B Improve~ 1 80 2C
B Improve~ 1 100 91 28
B mprove~ 1 (ai) 99 7
3~ B mprove~ 2 91 4~
B mprove~ 2 8 3 3 8
B Improve~ 2 100 88 48
B Improve~ .5(ai)

WO 95/12977 ~ ~ 73~ 6 ~ PCT/USg4/11731
+glycerin 1 ai)73 3 7
E Improve~ . ,(a ) 97 93
- E Improve~ .5(a ) 97 8 6 54
C mprove~ .~(ai) 100 9 9 93
5 C mprove~ ~(a ) 97 97
C mprove~ . ,(a) 100 83 38
C Improve~ .5(a )
+glycerin 1 (ai) 68 44
D Improve~ .5(ai) 100 99 92
10 'rABLE
cont'd
~FOR I Ad juvant Adj 16 8 4 2
%
D Improve~ .j(ai) 100 96
D mprove~ . ~(a ) 92 37 21
~5 D mprove~ . ,(a )
+glycerin 1 (ai~ 88 80 51
A Improve~ .5(ai) 97 8 8 59
F Improve~ .5 100 8 7
F Improve~ . (ai) 19
ao F Improve~ .,(ai) 76 46
F Improve~ 1 100 9 4
B MO~I 0818 .25 42 26
B MO\I 0818 .25 6 9 22
B MO~10818 1 35 13
B 28% \ 42 6
B 28% \ 2 5 6 12
B nonyphenol 4EO .5(a ) 11 9
B nonylphenol 6EO .5(a ) 20 18
B nonyp1enol 8EO .5(a ) 29 4
~ nonyplenol 10EO .5(a) 18 8
B nonyp1enol 12EO .5(a) 38 9
B R-11 .06 33 13
B R-11 .25 28 10
B Silwet L77 .25(ai) 2 2 11
B Silwet L77 .5 2 4 15
B Silwet L77 1 18 23
B Silwet L77 2 23p 9p

W095/12~77 217 31~ 0 rcTluss4lll73l
28
B S wet L77 ~ 62p 26p
B S wet L77 ~ 48p 32p
B S wet L77 .25
TABLE,
cont' d
*FOR I Ad juvant Adj 16 8 4 2
%
+MON 0818 .25 5 4 22
B Silwet L77 .5
~MON 0818 .25 4 7 18
B Sur ynol 465 1 18 15
B Sur-ynol 465 5 33p 5p
B Surfyno 485 .25(ai) 6 7 11
B Surfyno 485 .25(ai) 5 7 14
2~ B Surfyno 485 .5(ai) 8 " 13
B Surfynol 485 1 (ai) 71 30
B Surfynol 485 1 (ai` 92 51
B Tergitol~ S-3.5(a ) 49 7
B Terg to ~ - ~-S--l .5(a ) l1 21
25 B ~erg to ~ -S-j . (a ) ~0 0
B ~ erg to ~ 15-S-7 .5(a ) 86 49
B Tergitol~ 15-S-7 .5(a ) 74 26
F Tergito ~ 15-S-7 .5(a ) 35
B Terg to ~ 15-S-9 .~(a ) 90 23
B Terg to ~ 1 ,-S-9 .5(a ) 91 58
B Terg to ~ 1 5-S-12 .5(a ) 8 8 9
B Tergitol~ 1 5-S-12 .5(ai) 100 78
B Tergitol~ 1 5-S-1 2 .5(ai) 96 58
B Terg to ~ 15-S-12 .5(a ) 96 60
B Terg to ~ 15-S-12 .5(a ) 83 54
C Tergitol~ 15-S-12 .5(ai) 97 76
C Tergitol~ 15-S-12 .5(ai) 97 80 37

W095/12977 ~ ~ ~3 i 6 ~ PCT/US94/1~731
C Tergitol~ 1 5-S-12 .5(ai)
+glycerin 1 (ai) 91 68 29
TABLE 2
cont'd
*FOR I Ad juvant Adj 16 8 4 2
%
D Tergitol~15-S-12 .,(ai) 99 88
D Terg tol~- -S-- 2 . ~(ai) 96 88 43
D Terg tol~,-S- 2 .~(ai)
+gly~-erin1 (ai) 95 55
B Terg tol~15-S-15 .5(a ) 67 49
B Terg tol~1 5-S-15 .5(a ) 7 4 5
B Tween 20 .25 3 6 7
B Varion .25(ai) 47 0
______________________________
p = phytotoxicity noted on foliage
20 Bol-lf~ce % control indicates statistically significant i~ velllent in
e~e control compared to I-B, at the same rate, with either no adjuvant
or Triton CS7, in the same test. Adj. % is as defined in Table I, except (ai)
in the % Adj column me~qn~ the volume of adjuvant noted in Table I is
adjusted for the concentration of adjuvant active ingredient.
The surface-active or metting agents identified above are sold under
the noted names as follows. APG~) is sold by Henkel APG, Arquad is sold
by Akzo, Chemical Division, Buffercide is sold by Custom Chemic~
Cayuse~) is sold by Wilbur-Ellis Co. Improve~) is sold by Dow-~ nco.
CropOil is available from various sources. Ethoquad is also sold by Akzo,
30 Chemical Division, Emcol is available from Witco Corp. Organics Div.,
28~o Nitrogen can be made from usual nitrogen cont~ining compounds.
Nonylphenol is sold by, for ex~mple, Witco S.A. R-11 is available from
Wilbur-Ellis Co. Silwet is from Union Carbide Corp., Special Chemicals
Div. Surfynol is a product of Air Products and Chemicals, Inc. Tergitol is

WO 95/12977 PCT/US94/11731
2 ~7 3 ~
also a product of Union Carbide C~orp., Industrial Chemicals Div. Tween
20 is from ICI Americas, Inc. Tritont~) is from Rohm and Haa- Co.
Varion is from Sherex Chemical Co., Inc.
The following methods are also used to evaluate adjuvants that are
5 combined with a compound of formula 1, specifically, for example,
N-(3,4,4-trifluoro-1-oxo-3-butenyl)glycine, for effectiven~ss in
controlling root knot nematodes (Meloidogyne incognita) on tomato roots
when the adjuvant plus compound mixture is applied to the foliage of
young plants. I
10 Tomato plants (cultivar `Rutgers') were grown one per pot in six cm
square plastic pots cont~ining a mixture of equal parts fine sand, coarse
sand, silt loam soil, and commercial potting medium.
Compound/adjuvant mixtures were prepared by ~ ling the colmpound to
water to achieve final conc~ntrations of 2400, 1200, and 600 ppm, and then
in~ the adjuvant to the solution to achieve a final concentr~tion of 0.5%
volume of adjuvant/volume of water. This single adjuvant cor centration
was used with all 3 rates of the test compound, unless otherwise specified.
When the tomato plants were 18-21 days old the test solutionls were
sprayed onto the leaves and stems using a track sprayer which
20 appro~rim~tes application procedures and volumes used in the field. The
track sprayer is calibrated to apply the test solution at a volume of 25
gallons per acre, resulting in application rates of the compound of 8, 4,
and 2 ounces active ingredient per acre. Three plants were sprayed for
each treatment and then were air dried and kept under fluore~cent lights
25 for 15-18 hours prior to inoculation. All plants then were inoc~lated with
mature root knot nematode eggs cont~ining J1 larvae, with 8,000 eggs per
plant applied in 5 ml of water onto soil at the stem base. Plant then were
incubated in a growth chamber at 27C and 60% RH with all replicate pots
randomized throughout the chamber. During the two weeks immediately
30 following application of the test mixtures all plants received sub-irrigation and the foliage was kept dry.

WO 95/12977 PCT/US94111731
31 ~7316~
Three to 7 days after treatment the plant foliage was ç~mined for
symptoms of phytotoxicity and ~ssi~ned a rating value of 0-3 where 0= no
~m~ge, 1= mild spotting or chlorosis, 2= moderate ~l~mAge but no
st~lnting, and 3= severe rl~m~e and st~mtin~. After three weeks
6 incubation as described above the plant roots were washed and nçm~tode
disease seventy was assessed. Each root system was rated individually
and a visual estim~te of the percent of the root system rl~m~ged by
nematode galling was determined and assigned a value of 0, 1, 3, 5, 10, 25,
50, 75 or 100% root ~l~m~e.

WO 95/12977 217 3 1 6 ~ PICT/US94/11731
32 1
ADJUVANTS TESTED
tr~de ~me chemical name concentr~tion
Atplus 258 alkylpolyglucoside 62C~o a.i.
5 CS-7 alkyl aryl polyethoxylate and Na salt
alkyl sulfo~te-l alkylate 60aO a.i.
Dodigen 226 cocoalkyldimethyl benzyl ammonium
chloride 60% a.i.
Dodigen 4022
EmcolXE 1656 alkoxylated fatty amine oxide 70~O a.i.
Empigen OB alkyldimethyl amine oxide 30~o a.i.
Ethylan CPG 945 modified alcohol alkoxylate 10C % a.i.
Flo-Mo 3153 ethoxylated fatty amine oxide 70~o a.i.
Genapol T250 fatty alcohol polyglycol ether 10C % a.i.
15 Improve fattyamine ethoxylate 64aO a.i.
+ ethoxylated nonylphenol 14ao a.i.
Kaomul 230 coco esterfied polyethoxyether 10C % a.i.
piperonyl butoxide 10C % a.i.
Rhodonat LMO coconut oil based sucroglyceride 10C % a.i.
RhodonatMLP704 modified LMO sucroglyceride 10C% a.i.
Simusol M52 stearic acid polyethoxylated 10C % a.i.
Ethoduomeen ethoxylated alkyl amine 10~ % a.i.
Ethomeen C-15 ethoxylated alkyl amine ~ mine 10C % a.i.
MANUFACTURERS OF ADJWANTS TESTED
Atplus 258 Imperial Chemical ILdustries
Triton CS-7 Rohm & Haas Co.
Dodigen 226 Hoechst AG
Dodigen 4022 Hoechst AG
30 EmcolXE 1656 Witco Corp.
Empigen OB Albright & Wilsons

WO 95/12977 21 7 3 ~ 6 ~ PCT~US94J1173~
33
Ethylan CPG 94 Harcros Chemicals Inc.
Flo-Mo 3153 Witco Corp.
Genapol T250 Hoechst AG
Improve DowElanco
5 Kaomul 230 KAO Spain
piperonyl butoxide Fluka Chemik~
Rhodonat LMO Rhone-Poulenc
Rhodonat MLP704 Rhone-Poulenc
Simusol M52 Seppic France
10 Ethoduomeen AKZO C~orp.
Ethomeen C-16 ALZO Corp.

WO 95/12977 PCT/US94/11731
3 ~ 4
Table 3. Mean percent root (l~m~e due to nematode gallin~ (%
disease), the standard deviation of that mean (std dev), the %I control of
root ~m~e (% control), and foliar phytotoxicity rating (0=nc phyto,
3=severe phyto) after treatment of tom~to plants with (MON 4 ;700)
5 mixed with the indicated adjuvants.
A d j u v a n t % di ease phytotox
D average stddev% control average
(0.5% v/v unless noted) qai/ha
CS-7 560 33.33 11.7950.00 1.67
280 66.67 11.790.00 1.00
Improve 560 20.00 7.07 70.00 12.00
280 28.33 16.5057.50 1.00
140 58.33 11.7912.50 0.67
Witco C5867 560 20.00 7.07 70.00 1.33
280 50.00 20.4125.00 0.67
140 50.00 0.00 25.00 i1.33
Dodigen 226 560 20.00 7.07 70.00 ¦2.67
280 41.67 11.7937.50 12.67
140 33.33 11.7950.00 2.33
Neodol 25-9 560 20.00 7.07 70.00 ¦1.67
280 58.33 11.7912.50 ,1.33
140 58.33 11.7912.50 0.67
Stepwet DF-90 560 20.00 7.07 70.00 11.67
280 41.67 11.7937.50 10.33
140 58.33 11.7912.50 10.33
Emcol XE 1656 560 41.67 11.7937.50 11.00
280 58.33 11.7912.50 1.67
140 66.67 11.790.00 1.00
Simusol M52 560 41.67 11.7937.50 10.67
280 66.67 11.790.00 0.33
140 66.67 11.790.00 0.67
CS-7 560 15.00 7.07 77.50 2.00
280 33.33 11.7950.00 0.67
Improve 560 6.00 2.94 91.00 2.67
280 15.00 7.07 77.50 2.33
140 41.67 11.7937.50 1.67
Ethylan CPG945 560 13.33 8.50 80.00 13.00
280 41.67 11.7937.50 2.33
140 58.33 11.7912.50 2.00
.lo~ ,dl MLP704 560 8.33 2.3687.50 2.67
280 33.33 11.7950.00 1.33
140 58.33 11.7912.50 0.67

WO95/12977 ~ 3 l~Q PCT/US94/11731
~5
.
A d j u v a n t % di- ease phytotox
D average stddev% controlaverage
(0.5% v/v unless noted) qai/ha
RhodonatLMO 560 33.33 11.7950.00 1.33
280 58.33 11.7912.50 0.67
140 66.67 11.790.00 0.33
Kaomul 230 560 15.00 7.07 77.50 1.67
280 33.33 11.7950.00 1.33
140 62.50 12.506.25 0.67
(3enapolT 560 5.00 0.00 92.50 2.67
280 15.00 7.07 77.50 1.67
140 41.67 11.7937.50 0.67
Atplus 258 560 6.00 2.94 91.00 1.67
280 10.00 0.00 85.00 0.67
140 41.67 11.7937.50 0.67
CS-7 560 4.33 0.94 93.50 1.00
280 15.00 7.07 77.50 0.67
Improve 560 1.67 0.94 97.50 1.67
280 6.00 2.94 91.00 2.00
140 28.33 16.5057.50 1.67
Flomo 3153 560 2.00 2.16 97.00 2.00
280 6.67 2.36 90.00 0.67
1 4033.33 11.7950.00 0.00
Ethomeen C15 0.3% + 560 0.33 0.4799.50 3.00
Tergitol 15S9 0.2%
280 3.33 2.3695.00 2.67
ao 140 41.67 11.7937.50 2.00
Ethoduomeen T25 560 1.00 0.0098.50 2.00
280 8.33 2.3687.50 2.33
140 41.67 11.7937.50 1.33
Ethomeen C15 0.18%+ 560 11.67 9.4382.50 2.67
Tergitol 15S12 0.12% +
Tergitol 15S9 0.2%
280 0.00 0.00100.00 3.00
140 0.00 0.00100.00 3.00
Tergitol 15S9 280 0.00 0.00100.00 3.00
140 0.00 0.00100.00 3.00
Empigen OB 560 3.00 0.0095.50 2.67
280 11.67 10.2782.50 2.67
140 33.33 11.7950.00 1.67
CS-7 560 3.67 1.8992.67 1.67
3~ 280 8.33 2.3683.33 1.33
-

WO 95/12977 217 3 ~ ~ ~ PCTIUS94/11731
36
Ad j u va n t % di ease phytotox
D averagestddev% control Pverage
(0.5% v/v unless noted) qai/ha
Improve 560 0.33 0.47 99.33 2.00
280 6.67 2.36 86.67 l 1.33
140 15.00 7.07 70.00 ! 1.00
Atplus 258 0.4% + 560 1.33 1.25 97.33 0.67
piperonyl butoxide 0.1%
280 5.00 0.00 90.00 l 0.33
1 40 6.67 2.36 86.67 1.00
Atplus 258 0.5% + 560 0.00 0.00 100.00 l 1.33
10 ammonium sulfate 2.0%
280 2.33 0.94 95.33 0.67
1 40 15.00 7.07 70.00 0.67
Atplus 258 0.5% 560 0.33 0.47 99.33 1.33
280 3.00 0.00 94.00 1.00
1 40 20.00 7.07 60.00 0.33
Improve 0.5% + ammonium 560 1.33 1.25 97.33 2.33
sulfate 2.0%
280 3.33 2.36 93.33 1.33
1 40 25.00 0.00 50.00 1.00
Improve 0.5% + piperonyl 560 3.67 0.94 92.67 1.67
butoxide 0.1%
280 8.33 2.36 83.33 2.00
1 40 41.67 11.79 16.67 1.00
CS-7 0.5% + piperonyl 560 2.33 0.94 95.33 1.00
butoxide 0.1%
ao 280 6.67 2.36 86.67 1.67
140 41.67 11.79 16.67 0.67
CS-7 560 6.67 2.89 87.00 2.33
280 28.33 20.21 43.00 1.33
Improve 560 6.00 3.61 88.00 1.67
280 15.00 8.66 70.00 1.33
1 40 41.67 14.43 17.00 0.67
Dodigen 4022 560 6.00 3.61 88.00 1.67
280 13.33 10.41 73.00 1 1.67
140 41.67 14.43 17.00 ' 1.00
Dodigen 4022 0.4% + Tween 560 5.00 0.00 90.00 2.00
20 0.1%
280 15.00 8.66 70.00 1 1.33
1 40 41.67 14.43 17.00 1.33

~ WO 95/12977 PCT~S94/11731
2 ~ 73I ~0
A d j U v a n t . % disease phytotox
D average stddev % control average
(0.5% v/v unless noted) ~ai/ha
Dodigen 40220.32% + 560 13.33 10.41 73.00 2.00
Tween 200.08% +
5 piperonyl butoxide 0.1%
280 41.67 14.43 17,00 1.33
140 58.33 14.43 -17.00 1.00
Tergitol 15-S-9 0.2% 560 6.67 2.89 87.00 2.00
280 20.00 8.66 60.00 1.33
140 41.67 14.43 17.00 2.00
Ethomeen C15 0.15% + 560 5.00 0.00 90.00 1.67
10 Tergitol 15-S-9 0.1%
280 15.00 8.66 70.00 1.33
140 41.67 14.43 17.00 1.00
Crop Life 5.0% 560 8.33 2.89 83.00 1.67
280 25.00 0.00 50.00 0.67
140 50.00 0.00 0.00 1.00
,5
ao

Representative Drawing