Note: Descriptions are shown in the official language in which they were submitted.
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SUBSTITUTED BENZOTHIOPYRANES SALTS AND THEIR USE AS HERBICIDES
BACKGROUND OF THE INVENTION
This invention relates to certain salts, compositions of said salts, and
methods of their
use for controlling undesirable vegetation.
The control of undesired vegetation is extremely important in achieving high
crop
efficiency. Achievement of selective control of the growth of weeds especially
in such
useful crops as rice, soybean, sugar beet, corn (maize), potato, wheat,
barley, tomato and
plantation crops, among others, is very desirable. Unchecked weed growth in
such useful
crops can cause significant reduction in productivity and thereby result in
increased costs to
the consumer. The control of undesired vegetation in noncrop areas is also
important. Many
products are commercially available for these purposes, but the need continues
for new
compounds which are more effective, less costly, less toxic, environmentally
safer or have
different modes of action.
EP 283,261 discloses heterocycles of Formula i as herbicides:
x
~Ra
~x2
i
wherein
X, X i and X2 are independently O or S;
R1 is a monocyclic or fused-bicyclic heterocyclic group optionally substituted
by one
or more groups selected from oxo, mercapto, halo, nitro, cyano, amino, mono-
or
dialkylamino, amido, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl,
haloalkoxy,
aryl, hydroxy, alkoxy, alkoxycarbonyl, alkylcarbonyl, mono- or
dialkylcarbamoyl, alkylthio, alkylsulfinyl, alkylsulfonyl, sufonamido,
alkylcarbonyloxy, alkylcarbonylamino or heterocyclyl; and
Y is, inter alia, C2-C4 alkylene.
The salts of the present invention are not disclosed in this reference.
SUMMARY OF THE INVENTION
This invention is directed to compounds of Formula I including all geometric
and
stereoisomers, agricultural compositions containing them and their use for
controlling
undesirable vegetation:
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7
R~ R2 R4 O
~ Q rf-
(R3)P M
(O)n RS
r
I
wherein
Q is
0
0
/ _-
(R6)q or ~ iN~ R7 ;
O
Q-1 Q-2
M is Li, Na, K, Ca, Mg, Co, Ni, Cu or Zn; or M is
R8
R9-N-R10
R11
r is 1 when M is Li, Na, K or
R8
R9-N-Rl~
Rl l
or
r is 2 when M is Ca, Mg, Co, Ni, Cu or Zn;
R 1 and R2 are taken together with the carbon to which they are attached to
form C(=O)
or R1 and R2 are taken together to form -OCH2CH20- optionally substituted
with one to two C1-C3 alkyl;
each R3 is CH3;
R4 and RS are each independently H, C1-C3 alkyl or halogen;
R6 is C 1-C3 alkyl;
R~ is C1-C3 alkyl;
Rg is H, C 1-C25 alkyl or benzyl;
R9 and R 1 ~ are independently C 1-C25 alkyl;
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R ~ ~ is C ~-C~5 alkyl or
R ~'-
O-(CH?)~; O-(CH~h-
R~'- is H, C~-CI~ alkyl, Cl-C3 alkoxy, NO~ or CN;
m and t are independently l, 2 or 3;
n and p are each independently 0, 1 or 2; and
q is 0, 1, 2, 3 or 4;
provided that
when Q is Q-1 and R t and R2 are taken together with the carbon to which they
are
attached to form C(=O), then n is 1 or 2.
In the above recitations, the term "alkyl", used either alone or in compound
words such
as "alkylthio" or "haloalkyl" includes straight-chain or branched alkyl, such
as, methyl,
ethyl, n-propyl, i-propyl, or the different butyl, pentyl or hexyl isomers.
"Alkoxy" includes,
for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different
butoxy, pentoxy
and hexyloxy isomers.
The term "halogen", either alone or in compound words such as "haloalkyl",
includes
fluorine, chlorine, bromine or iodine.
The total number of carbon atoms in a substituent group is indicated by the
"C;-Cj"
prefix where i and j are numbers from 1 to 25. For example, C~-C3 alkyl
designates methyl
through propyl.
When a compound is substituted with a substituent bearing a subscript that
indicates
the number of said substituents can exceed 1, said substituents (when they
exceed 1 ) are
independently selected from the group of defined substituents.
When a group contains a substituent which can be hydrogen, for example R~2,
then,
when this substituent is taken as hydrogen, it is recognized that this is
equivalent to said
group being unsubstituted.
Compounds of this invention can exist as one or more stereoisomers. The
various
stereoisomers include enantiomers, diastereomers, atropisomers and geometric
isomers. One
skilled in the art will appreciate that one stereoisomer may be more active
andlor may exhibit
beneficial effects when enriched relative to the other stereoisomer(s) or when
separated from
the other stereoisomer(s). Additionally, the skilled artisan knows how to
separate, enrich,
and/or to selectively prepare said stereoisomers. Accordingly, the present
invention
comprises compounds selected from Formula I and agriculturally suitable salts
thereof. The
compounds of the invention may be present as a mixture of stereoisomers,
individual
stereoisomers, or as an optically active form.
Some compounds of this invention can exist as one or more tautomers. One
skilled in
the art will recognize, fox example, that compounds of Formula Ia (Formula I
where Q is
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WO 98l28291 PCT/(JS97/23469
Q-1 ) can also exist as other tautomers as shown below. One skilled in the art
will recognize
that said tautomers often exist in equilibrium with each other. As these
tautomers
interconvert under environmental and physiological conditions, they provide
the same useful
biological effects. The present invention includes mixtures of such tautomers
as well as the
individual tautomers of compounds of Formula I.
R~ R2 R4 O O Na+
\ /
(R3)P ~ (R6)q
(O)n RS O
Ia
wherein M is Na
RI R2 R4 O + O Rl R2 R4 O Na+ O
Na
\ ~C \
(R3)P ~ (R~y -r ~ (R3)P ~~~~ ~ ~~(R~4
RS O (O)n RS O
Preferred compounds for reasons of better activity and/or ease of synthesis
are:
Preferred 1. Compounds of Formula I above wherein:
Q is Q-1.
Preferred 2. Compounds of Preferred 1 wherein:
R4 and RS are each independently H or CI-C3 alkyl;
nis2;
p is 0; and
qis0, 1 or2.
Preferred 3. Compounds of Preferred 2 wherein:
M is
Rg
R9-N-R~0
RI I
Preferred 4. Compounds of Preferred 2 wherein:
M is Li, Na or K.
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J
Preferred 5. Compounds of Formula I above wherein:
Q is Q_~.
- Preferred 6. Compounds of Preferred 5 wherein:
R'1 and R~ are each independently H or C~-C; alkyl;
R~ is CHZCH;;
n is 2;
pis0;and
qis0, 1 or2.
Preferred 7. Compounds of Preferred 6 wherein:
M is
R8
R9-N-R10
R11
Preferred 8. Compounds of Preferred 6 wherein:
M is Li, Na or K.
Most preferred are the compounds of Formula I selected from the group of the
lithium, sodium, and potassium salts of:
a) 2-[(3,4-dihydro-5,8-dimethyl-4-oxo-2H I-benzothiopyran-6-yl)carbonyl]-5,5-
dimethyl-1,3-cyclohexanedione S,S-dioxide;
b) 2-[(2,3-dihydro-5,8-dimethylspiro[4H I-benzothiopyran-4,2'-[1,3]dioxolan]-6-
yl)carbonyl]-1,3-cyclohexanedione S,S dioxide;
, c) (2,3-dihydro-5,8-dimethylspiro[4H 1-benzothiopyran-4,2'-[1,3]dioxolan]-6-
yl)( 1-ethyl-5-hydroxy- I H pyrazol-4-yl)methanone S,S-dioxide; and
d) 6-[{ 1-ethyl-5-hydroxy-1 H pyrazol-4-y1)carbonyl]-2,3-dihydro-5, 8-dimethyl-
4H
1-benzothiopyran-4-one 1,1-dioxide.
This invention also relates to herbicidal compositions comprising herbicidally
effective
amounts of the compounds of the invention and at least one of a surfactant, a
solid diluent or
a liquid diluent. The preferred compositions of the present invention are
those which
comprise the above preferred compounds.
This invention also relates to a method for controlling undesired vegetation
comprising
applying to the locus of the vegetation herbicidally effective amounts of the
compounds of
the invention (e.g., as a composition described herein). The preferred methods
of use are
those involving the above preferred compounds.
DETAILS OF THE INVENTION
The compounds of Formula I can be prepared by one or more of the following
methods
and variations as described in Schemes 1-13. The definitions of Q, R 1-R 1',
M, m, n, p, q,
and r in the compounds of Formulae 1-11 below are as defined above in the
Summary of the
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6
Invention. Compounds of Formulae Ia and Ib are subsets of the compounds of
Formula I,
and a11 substituents for Formulae Ia and Ib are as defined above for Formula
I. For example,
compounds of Formula Ia below are compounds of Formula I wherein Q is Q-1.
M r+
r
Ia
Scheme 1 illustrates the preparation of compounds of Formula Ia whereby an
enol of
Formula 1 is treated with an alkali metal alkoxide in an alcoholic solvent
such as methanol
or ethanol. When M is Ca or Mg, compounds of Formula Ia may be prepared by the
treatment of an enol of Formula 1 with a calcium or magnesium alkoxide. When M
is a
quaternary ammonium salt, compounds of Formula Ia may be prepared by the
treatment of
an enol of Formula 1 with a suitable quaternary ammonium halide salt and a
base. This
conversion is carried out by methods are known in the art (or by slight
modification of these
methods).
Scheme 1
alkali alkoxide or
Ca or Mg alkoxide or
(R (R6)q Ia
quaternary ammonium
salt and base
Scheme 2 illustrates the preparation of compounds of Formula 1 b (R I and R2
are taken
together with the carbon to which they are attached to form C(=O)) whereby a
compound of
Formula 1 a (Rl and R2 are taken together to form -O(CH2)~O- optionally
substituted with
one or two C I-C3 alkyl) is stirred in hydrochloric acid or hydrobromic acid
aqueous solution
(0.1 N to 12 N) at temperatures between 0 ~C and 100 ~C for a period of time
ranging from
minutes to 3 days. This conversion is carried out by methods known in the art
{or by
slight modification of these methods): for example; see P. A. Grieco, et al.,
J. Am. Chem.
Soc. ( 1977), 99, p S773; P. A. Grieco, et al., J. Org. Chem. ( 1978), 43, p
4178.
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WO 98I28291 PCT/US97/23469
7
Scheme 2
R ~ R? R4 O OH
\ / HCl/H~O
(R3)P ~ (R6)9 a
RS O or HBr/H20
(O)n
la
R 1 R2 R4 O OH
(R1 and R2 are taken
together to form -O(CH2)20- \ /
optionally substituted with (R3)p 1 //~(R6)q
one or two C 1-C3 alkyl ,~~\/J)
(Oh, RS O
lb
(R1 and R2 are taken together with the
carbon to which they are attached to
form C(=O))
Scheme 3 illustrates the preparation of a compound of Formula 1 a whereby an
enol
ester of Formula 2 is reacted with a base such as triethylamine in the
presence of a catalytic
amount of a cyanide source (e.g., acetone cyanohydrin or potassium cyanide) );
standard
acidic workup procedures then yield the compound of Formula 1 a.
Alternatively, the
triethylammonium salt of 1 a can be isolated directly; this method is
preferred for
compounds which may be sensitive to the acidic workup conditions. Treatment of
the
triethylammonium salt of 1 a with aqueous alkali metal hydroxides yields the
corresponding
alkali metal salt of Formula Ia. The cyanide-catalyzed rearrangement is carned
out by
general methods known in the art; see for example, W. J. Michaely, EP 0369803-
A1; D.
Cartwright, et al., EP 0283261-B1.
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WO 98/28291 PCT/US97/23469
8
Scheme 3
0
(R6)G
O
Base (e.g., triethylamine)
la
Cyanide source in catalytic
amount (e.g., acetone cyano-
hydrin or potassium cyanide)
S Enol esters of Formula 2 can be prepared by reacting a dicarbonyl compound
of
Formula 3 with an acid chloride of Formula 4 in the presence of a slight molar
excess of a
base such as triethylamine in an inert organic solvent such as acetonitrile,
methylene chloride
or toluene at temperatures between 0 ~C and 110 ~C (Scheme 4). This type of
coupling is
carried out by general methods known in the art (or by slight modification of
these methods):
for example, see W. J. Michaely, EP 0369803-A1; D. Cartwright, et al., EP
0283261-B1.
Scheme 4
O R1 R2 R4 O
~, ~ CI
(R~q + (R')p
O S RS
(O)n
4
Base (e.g., triethylamine)
The acid chlorides of Formula 4 can be prepared by reacting an acid of Formula
5
with oxalyl chloride (or thionyl chloride) and a catalytic amount of N,N-
dimethylformamide
(DMF) (Scheme 5). This chlorination is well known in the art; see for example,
W. J.
Michaely, EP 0369803-A1.
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WO 98l28291 PCTlUS9?/23469
9
Scheme 5
Rl ~~ R4 O
oxalyl chloride or
OH thionyl chloride ~ SCI
(R~)P
catalytic amount
of DMF s R~
v..~m (O~
4
5
Alternatively, compounds of Formula 2 can be prepared directly from the acids
of
Formula 5 by treatment with an alkyl chloroformate, followed by reaction of
the formed
intermediate mixed anhydrides with the dicarbonyl compounds of Formula 3.
Scheme 6 illustrates the preparation of acids of Formula 5 (n is I or 2)
whereby an acid
of Formula 5 (n is 0) is reacted with a oxidizing reagent such as peroxyacetic
acid,
m-chloroperoxybenzoic acid, potassium peroxymonosulfate or hydrogen peroxide.
The
reaction may be buffered with a base such as sodium acetate or sodium
carbonate. The
oxidation is carried out by general methods known in the art (see for example,
B. M. Trost,
et al., J. Org. Chem. (1988), 53, S32; B. M. Trost, et al., Tetrahedron Lett.
(1981), 21, 1287;
S. Patai, et aL, The Chemistry of Sulphones and Sulphoxides, John Wiley &
Sons).
Scheme 6
5 (n is 0) 5 (n is 1 or 2)
oxidizing agent
Scheme 7 illustrates the preparation of acids of Formula 5 (n is 0) whereby a
phenyl
bromide of Formula 6 (R 1 and RZ are other than taken together with the carbon
to which they
are attached to form C(=O) and n is 0) is treated with n-butyllithium (or
magnesium), and the
lithium salt (or the Grignard reagent) generated in situ is then reacted with
carbon dioxide
followed by acidification with an acid such as hydrochloric acid. This
conversion is carried
out by general methods known in the art; see for example, M. A. Ogliaruso et
al., Synthesis
of Carboxylic Acids, Esters and Their Derivatives, pp 27-28, John Wiley &
Sons; A. J.
Bridges, et al., J. Org. Chem. (1990), 55 (2), 773; C. Franke, et al., Angew.
Chem. Int. Ed.
( I 969), 8, 68. In some instances, the incorporation of
protection/deprotection sequences or
functional group interconversions into the synthesis will aid in obtaining the
desired
products. The use and choice of the protecting groups will be apparent to one
skilled in
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WO 98/28291 PCT/US9?/23469
chemical synthesis (see, for example, Green, T. W.; Wuts, P. G. M., Protective
Groups in
Organic Synthesis, 2nd ed.; Wiley: New York, 199l ).
Scheme 7
Rl RZ R4 . ~ ) n-BuLi (or Mg)
Br ~) CO~
(R')p I 5 (n is 0)
3) H30+
(O~ R
6
(R 1 and RZ are other than taken
together with the carbon to which
they are attached to form C(=O) and
n is 0)
Scheme 8 illustrates the preparation of phenyl bromides of Formula 6 (R 1 and
R2 are
taken together to form -O(CH2)20- optionally substituted with one or two C 1-
C3 alkyl and n
10 is 0) whereby a ketone of Formula 7 (n is 0) is reacted with HO(CH2)20H in
the presence of
a protic acid catalyst such as p-toluenesulfonic acid (or a Lewis acid such as
BF3) in an inert
organic solvent such as toluene. This conversion is carried out by general
methods known in
the art; see for example, T. W. Greens, et al., Protective Groups in Organic
Synthesis
(Second Edition), pp 1?5-221, John Wiley & Sons, Inc.
Scheme 8
O R4
HOCH2CH20H optionally
Br substituted with one or
~3) ~ two Cl-G3 alkyl
p 6 (n is 0)
(catalytic amount of acid)
RS
7 (n is 0)
Some compounds of Formula 7 (n is 0) can also be prepared by reacting a
substituted
benzene of Formula 8 (n is 0) with bromine in an inert organic solvent (Scheme
9). This
bromination is carried out by general methods known in the art. See E.
Campaigns, et al.,
J: Heterocycl. Chem. (1969), 6, p 517; H. Gilman, J. Am. Chem. Soc. (195S),
77, p 6059.
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WO 98I28291 PCT/US97/23469
Scheme 9
D
R1 R' R4
Br
(R > (R3)
P
RS
(~)n
8 7
(n is 0) (n is 0)
The ketones of Formula 7 can also be prepared by general methods known in the
art
(or by slight modification of these methods); see, for example, W. Flemming,
et al., Chem.
Ber. (1925), 58, l612; I. W. J. Still, et al., Can. J. Chem. (l976), 54, 453-
470; V. J.
Traynelis, et al., J. Org. Chem. ( 1961 ), 26, 2728; I. Nasuno, et al., WO
94/08988; F. Camps,
et al., J. Heterocyct. Chem. ( 198S), 22(5), p. 1421; T. S. Rao, et al.,
Indian J. Chem. B.
{1985), 24(11), p. 1159; S. Ghosh, et al., Tetrahedron (1989), 45{5), p. 1441;
A. Danan,
et al., Synthesis-Stuttgart ( 1991 ), ( 10), p. 879; P. Magnus, et al., J.
Chem. Soc. Chem. Comm.
( 1991 ), (7), p. 544; A. Padwa, et al., J. Org. Chem. ( 1989J, 54( 12), p.
2862; S. A. Ali, et al.,
J. Org. Chem. (1979), 44, p. 4213; J. Blake, et al., J. Am. Chem. Soc. (1966),
88, p. 4061;
M. Mori, et al., J. Chem. Soc. Chem. Comm. ( 1990), ( 18 ), p. 1222; S. Kano,
et al., J. Chem.
Soc., Perkin. Traps. 1 (1980), p. 210S; A. F. Bekhli, et al., Khim
Geterotsikl. Soedin. (1975),
p. 1118; W. S. Johnson, et al., J. Am. Chem. Soc. ( 1949), 71, p. 190I ; J. A.
Hirsch, et al., J.
Org. Chem. ( 1974), 3 9( 14), p. 2044; F. G. Mann, et al., J. Chem. Soc. (
1957), p. 4166;
A. C. Jain, et al., Indian. J. Chem. B ( 1987), 2b(2), p. 136; G. Ariamala, et
al., Tet. Lett.
(1988), 29(28), p. 348?; B. Loubinoux, et al., Tet. Lett. (1992), 33(16), p.
2145; S. Cabiddu,
et al., J. Organomet. Chem. ( 1989), 366{ 1-2), p. 1; R. HasenKamp, et al.,
Chem. Ber. ( 1980),
113, p. 1708; D. A. Pulman, et al., ,l. Chem. Soc. Perkin. Traps. 1 (1973), p.
410;
W. C. Lumma, et al., J. Org. Chem. (l969), 34, p. l566; P. D. Clark, et al.,
Can. J. Chem.
(l982), 60(3), p. 243.
Compounds of Formula 8 can be prepared by one skilled in the art by using the
reactions and techniques known in the art. The dicarbonyl compounds of Formula
3 are
either commercially available or can be prepared by general methods known in
the art {or by
slight modification of these methods): for example, see D. Cartwright, et al.,
EP 028326l -
B1; J. Dangelo, et al., Tet. Lett. (I991), 32(26), p. 3063; T. Okado, et al.,
J. Org. Chem.
( 1977), 42, p. 1163; B. E. Maryanoff, et al., J. Am. Chem Soc. ( l975), 97,
p. 2718; E. Er,
et al., Helv. Chim. Acta. (1992), 75(7), p. 2265; Y. D. Vankar, et al., Tet.
Lett., {1987), 28(5),
p. 551; C. S. Pak, et al., Tet. Lett. ( I 99I ), 32(42), p. 6011; I.
Nishiguchi, et al., Chem. Lett.
( 1981 ), p. 551; B. Eistert, et al., Liebigs Ann. Chem. ( 1962), 659, p. 64;
N. K. Hamer, Tet.
CA 02270245 1999-04-28
WO 98I28291 PCT/LTS97/23469
I?
Lett. ( 1986)) 27( I 9), p. 2167; M. Sato) et al., Heterocycles ( I 987), 26(
10), p. 26l 1;
A. Murray, et ai., Tet. Lett. { 1995 ), 36(2), p. 291; K. S. Kochhar, et al.,
Tet. Lett. ( 1984),
25( 18), p. I 87I ; M. Sato, et ai., Tetrahedron ( 1991 ), 47(30), p. 5689; M.
Sato, et al., Chem.
Pharm. Bull. ( I 990), 38( 1 ), p. 94; T. Meal, U.S. 4,93 l,570; T. Muel, et
al., U.S. 5,093,503.
Compounds of Formula Ib can be readily prepared by one skilled in the art by
using
the reactions and techniques described in Schemes 10-13 of this section as
well as by
following the specific procedures given in Example 1.
N-R7 I M ~
r
Ib
Scheme 10 illustrates the preparation of compounds of Formula Ib from
compounds of
Formula 9. Reaction conditions are as described for Scheme 1.
Scheme 10
R7 alkali alkoxide or Ib
quaternary ammonium
salt and base
9
Scheme I I illustrates the preparation of compounds of Formula Ib whereby an
ester of
Formula 10 is reacted with a base such as triethylamine in the presence of a
catalytic amount
of cyanide source (e.g., acetone cyanohydrin or potassium cyanide). This
rearrangement is
carried out by methods known in the art; see for example, W. J. Michaely, EP
0369803-A1.
u4 n
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13
Scheme 11
RI R, R4 O R \Ni \
~H
~O
(R3)p , Base (e.~., triethylamine}
Ib
RS Cyanide source in catalytic
O
amount (e.g.) acetone cyano-
hydrin or potassium cyanide)
5 Scheme 12 illustrates the preparation of compounds of Formula Ib {RI and R2
are
taken together with the carbon to which they are attached to form C(=O))
whereby a
compound of Formula Ib (RI and R~ are taken together to form -O(CH2)20-
optionally
substituted with one or two CI-C3 alkyl) is stirred in a hydrochloric acid or
hydrobromic acid
aqueous solution (0.1N to 1211 at temperatures between 0 ~C and 100 ~C for a
period of time
10 ranging from 30 minutes to 3 days. This conversion is carried out by
methods known in the
art (or by slight modification of these methods): for example; see P. A.
Grieco, et al., J. Am.
Chem. Soc. ( 1977), 99, p S773; P. A. Grieco, et al, J. Am. Chem. Soc. (
1978), 43, p 4178.
Scheme 12
HCI/H20
9 -,----~ 9
or HBr1H20
(RI and R2 are taken together (RI and R2 are taken together with the
to form -O(CH2~0- optionally carbon to which they are attached to
substituted with one or two form (C=O))
CI-C3 alkyl)
Esters of Formula 10 can be prepared by reacting a hydroxypyrazole of Formula
11
with an acid chloride of Formula 4 in the presence of a slight molar excess of
a base such as
triethylamine in an inert organic solvent such as acetonitrile,
dichloromethane or toluene at
temperatures between 0 ~C and 110 ~C (Scheme 13). This type of coupling is
carried out by
methods known in the art; see for example, W. J. Michaely, EP 0369803-A1.
CA 02270245 1999-04-28
WO 98I28291 PCT/US97/23469
1.~
Scheme 13
H
N base
HO N~ (e.~., triethylamine)
5 It is recognized that some reagents and reaction conditions described above
for
preparing compounds of Formula I may not be compatible with certain
functionalities
present in the intermediates. In these instances, the incorporation of
protection/deprotection
sequences or functional group interconversions into the synthesis will aid in
obtaining the
desired products. The use and choice of the protecting groups will be apparent
to one skilled
10 in chemical synthesis (see, for example, Greene, T. W.; Wuts, P. G. M.
Protective Groups in
Organic Synthesis, 2nd ed.; Wiley: New York, 1991 ). One skilled in the art
will recognize
that, in some cases, after the introduction of a given reagent as it is
depicted in any individual
scheme, it may be necessary to perform additional routine synthetic steps not
described in
detail to complete the synthesis of compounds of Formula I. One skilled in the
art will also
recognize that it may be necessary to perform a combination of the steps
illustrated in the
above schemes in an order other than that implied by the particular sequence
presented to
prepare the compounds of Formula I.
One skilled in the art will also recognize that compounds of Formula I and the
intermediates described herein can be subjected to various electrophilic,
nucleophilic,
radical, organometallic, oxidation, and reduction reactions to add
substituents or modify
existing substituents.
Without further elaboration, it is believed that one skilled in the art using
the preceding
description can utilize the present invention to its fullest extent. The
following Examples
are, therefore, to be construed as merely illustrative, and not limiting of
the disclosure in any
way whatsoever. Percentages are by weight except for chromatographic solvent
mixtures or
where otherwise indicated. Parts and percentages for chromatographic solvent
mixtures are
by volume unless otherwise indicated. The abbreviation "dec" indicates that
the compound
appeared to decompose on melting. 1 H NMR spectra are reported in ppm
downfield from
tetramethylsilane; s = singlet, d = doublet, t = triplet, q = quartet, m =
multiplet, br s = broad
singlet.
CA 02270245 1999-04-28
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I~
Example 1
Step A: Preparation of 3-f12.5-dimethYphenvl)thiolpropanoic acid
43.4 g ( I .086 mol) of sodium hydroxide was added to 230 mL of water) 75.0 g
(0.543
mol) of 2.5-dimethylthiophenol (purchased from Aldrich Chemical Company) was
then
added and the mixture was cooled to about 10 ~C. 91.30 g (0.597 mol) of 3-
bromopropionic
acid (purchased from Aldrich Chemical Company) was added in portions while
keeping the
temperature below 25 ~C. The mixture was warmed to room temperature, stirred
for 2 h
under nitrogen, and was then washed with diethyl ether (3 x 500 mL). The
aqueous layer
was acidified with 1 N HCI and filtered to yield 112.79 g of the title
compound of Step A as a
I 0 solid melting at 97-98 ~C. ~ H NMR (CDCl3): 8 2.3 {s,3H), 2.34 (s,3H),
2.68 (t,2H), 3.1
(t,2H), 6.9 (d, l H), 7.06-7.14 (2H).
Step B: Preparation of 2,3-dihvdro-5,8-dimethyl-4H 1-benzonvran-4-one
530 mL of concentrated sulfuric acid was added to 24.9l g (0.119 mol) of the
title
compound of Step A while being cooled with an acetone/ice bath. The ice bath
was
15 removed, the mixture was stirred for 1 h and was then poured over crushed
ice. The aqueous
mixture was extracted with a 1 : 9 mixture of diethyl ether : hexane (6 x 500
mL), dried
(MgSO~), filtered, and evaporated to dryness to yield 11.75 g of the title
compound of
Step B as an oil. ~ H NMR (CDC13): 8 2.3 (s,3H), 2.6 (s,3H}, 2.97 (m,2H), 3.2
(m,2H),
6.9-7.1 (2H).
20 Sten C: Preparation of 6-bromo-2,3-dihydro-5~8-dimethvl-4H 1-
benzothi.opyran-4-
one
A solution of 4.0? g (0.021 mol) of the title compound of Step B in 25 mL of
methylene chloride was added dropwise to a mixture of 7.07 g (0.0S 3 mol) of
aluminum
chloride (purchased from Aldrich Chemical Company) and 25 mL of methylene
chloride.
25 The suspension was stirred for approximately ~15 minutes, 1.14 mL {0.022
mol) of bromine
(purchased from Janssen) was added dropwise, and the mixture was refluxed for
10 minutes.
The warm mixture was poured into 10 mL of concentrated hydrochloric acid
containing 75 g
of ice, stirred for 10 minutes, diluted with 50 mL of water, and then
extracted with diethyl
ether (2 x 200 mL). The combined organic layers were washed with water (2 x
200 mL),
30 dried (Na2S04), filtered, and evaporated to dryness. The crude product was
chromatographed over silica gel eluting with a mixture of ethyl acetate :
hexane (5% : 95%)
to yield 2.62 g of the title compound of Step C as a solid melting at 87-88
~C. ~ H NMR
(CDCl3): 8 2.3 (s,3H), 2.6 (s,3H), 3.0 (m,2H), 3.2 (m,2H), 7.45 (s,lH).
Sten D:D: Preparation of 6-bromo-2.3-dihydro-5L8-dimethylspiro[4H 1-
benzothionyran-
35 42'-(1,3,Jdioxolane]
26.06 g (0.096 mol) of the title compound of Step C, 250 mL of ethylene
glycol, 170
mL of trimethyl orthoformate (purchased from Aldrich Chemical Company), and
0.06 g of
p-toluenesulfonic acid monohydrate were stirred together at 80 ~C under
nitrogen overnight.
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WO 98/28291 PCT/US97/23469
16
The mixture was diluted with 400 mL of diethyl ether. The resulting mixture
was washed
with a 1:1 mixture of 1 N sodium hydroxide: saturated aqueous NaCI (2 x 600
mL) and then
with saturated aqueous NaCI ( 1 x 600 mL). The organic layer was dried
(Na~SO~), filtered,
and evaporated to dryness. The crude product was chromatographed over silica
gel eluting
with a mixture of ethyl acetate : hexane ( 1 : 9) to yield 24.73 g of the
title compound of
Step D as a solid melting at 97 ~C (dec). ~H NMR (CDC1;): b 2.2 (s,3H), 2.3
(m.2H), 2.4
(s,3 H), 3.0 (m,2H), 4.15 (m,2H), 4.3 (m,2H), 7.3 (s, l H).
Step E: Preparation of 2,3-dihydro-5,8-dimethylspiro[4H 1-benzothiopyran-4 2'-
Il,3~dioxolanel-6-carboxylic acid
24.73 g (0.078 mol) of the title compound of Step D was added to 150 mL of
tetrahydrofuran. The solution was cooled to about -70 ~ under nitrogen and
37.68 mL (0.094
mol) of 2.5M n-butyllithium in hexane was added dropwise while keeping the
temperature
below -65 ~C. After stirnng for i h, carbon dioxide was bubbled into the
mixture for 2 h.
The mixture was allowed to warm to room temperature, 300 mL of hexanes were
added, and
the resulting mixture was filtered. The resulting solid was added to a mixture
of water
methylene chloride (400 mL : 400 mL), cooled to about 0 ~C, and acidified to
pH 1 with
concentrated hydrochloric acid. The layers were separated and the aqueous
layer was
extracted with diethyl ether (2 x 300 mL). The combined organic layers were
dried
(MgS04), filtered, and evaporated to dryness to yield 4.73 g of the title
compound of Step E
as a solid melting at 207-208 ~C. t H NMR (Me2S0-d6): 8 2.2 (m,SH), 2.4
(s,3H), 3.0
(m,2H), 4.1-4.2 (m,4H), 7.4 (s, l H).
St_ ep F: Preparation of 2,3-dihydro-5 8-dimethylspiro[4H 1-benzothiopyran-
4,2'-
j I (3ldioxolane]'-6-carboxylic acid 1, I-dioxide
4.73 g (0.017 mol) of the title compound of Step E and 2.08 g (0.025 mol) of
sodium
acetate were added to 85 mL of methanol. The solution was cooled to about 0
~C, and a
solution of 17.66 g (0.029 mol) of OXONE~ (purchased from Aldrich Chemical
Company)
in 85 mL of water was added dropwise while keeping the temperature below 6 ~C.
The
mixture was warmed to room temperature and stirred under nitrogen overnight.
The mixture
was diluted with 50 mL of water, cooled to about 0 ~C, acidified to around pH
2 with
concentrated hydrochloric acid, and then extracted with chloroform (3 x 150
mL). The
combined organic layers were dried (MgSOq), filtered, and evaporated to
dryness. The
residue was triturated in diethyl ether : hexane ( 1 : 9) which was decanted
to yield 4. I 8 g of
the title compound of Step F as a solid melting at 185 ~C (dec). ~ H NMR
(Me2S0-d6): 8
2.35 (s,3H), 2.5 (m,2H), 2.6 (s,3H), 3.5 (m,2H), 4.16 (m,2H), 4.2 (m,2H), 7.6
(s,IH).
Steo G: Preparation of 1-ethyl-1H pyrazol-5-yl 2.3-dihydro-5,8-
dimethylspiro[4H 1-
benzothiopyran-4,2'-f 1,3ldioxolane~-6-carboxylate 1, I -dioxide
1.18 g (3.8 mmol) of the title compound of Step F, 0.99 mL (0.011 mol) of
oxalyl
chloride (purchased from Janssen), and 2 drops of N,N dimethylformamide were
added to 50
CA 02270245 1999-04-28
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17
mL of methylene chloride. The mixture was retluxed under nitrogen for 2 h, and
was then
evaporated to dryness. ~0 mL of methylene chloride was added to the residue
and the
resulting mixture was evaporated to dryness. Another 50 mL of methyiene
chloride was
added to the residue, and the solution was cooled to about 0 ~C. 0.5l g (4.~
mmol) of I-
ethyl-1H pyrazoi-5-of was added followed by 1.63 mL (0.012 mol) of
triethylamine, and the
mixture was stirred overnight while warming to room temperature. The mixture
was
evaporated to dryness and the crude product was chromatographed eluting with a
mixture of
ethyl acetate : hexane {6 : 4) to yield 0.24 g of the title compound of Step G
as a semi-solid.
~H NMR (CDC1;): S 1.4 (t,3H), 2.5 (s,3H), 2.6 (m,2H), 2.8 (s,3H), 3.5 (m,2H),
4.1-4.4
I 0 (m,6H), 6.26 (s, l H), 7.5-7.7 (2H).
Step H: Preparation of (2,3-dihvdro-5,8-dimethylspiro[4H I-benzothiopyran-4 2'-
jl ,3ldioxolanl-6-yl)( 1-ethyl-S-hvdrox~ I H pyrazol-4-yl)methanone S. S
dioxide
0.24 g (0.59 mmol) of the title compound of Step G, 0.25 drops of acetone
15 cyanohydrin (purchased from Aldrich Chemical Company), and 0.14 mL ( I .0
mmol) of
triethylamine were added to 25 mL of acetonitrile and the mixture was allowed
to stir at
room temperature under nitrogen for I .5 h. About 0.06 g of potassium cyanide
was added to
the mixture which then was stirred at room temperature overnight. The mixture
was
evaporated to dryness and water was added to the residue. The resulting
mixture was
20 acidified to pH 1 with concentrated hydrochloric acid and extracted with
methylene chloride
(2 x 50 mL). The combined organic layers were dried (MgS04), filtered, and
evaporated to
dryness to yield 0.17 g of the title compound of Step H as a solid melting at
111 ~C (dec).
tH NMR (CDCl3): 8 1.46 (t,3H), 2.3 (s,3H), 2.6 (m,2H), 2.8 {s,3H), 3.5 (m,2H),
4.1 (q,2H),
4.2-4.3 (m,4H), 7.3 (2H).
25 Step I: Preparation of (2,3-dihydro-5,8-dimethvlspiro[4H I-benzothiopvran-
4~2'-
j 1,3ldioxolanl-6-yl)yl -ethyl-S-hvdroxy-1 H=pyrazol-4-yl)methanone S. S-
dioxide monopotassium salt
600 mg of the title compound of Step H, 105 mg of potassium methoxide, and 40
mL
of methanol were added to a flask and the resulting mixture was stirred at
room temperature
30 overnight under a nitrogen atmosphere. The reaction mixture was then
concentrated under
reduced pressure and the residue was triturated with ether. The resulting
solid was collected
by filtration and dried under vacuum overnight to yield 630 mg of the title
compound of Step
I, a compound of this invention, as a solid melting at >260 ~C.
Example 2
35 Steo A: Preparation of 3-oxo-I-cyclohexen-1-yl 2.3-dihydro-5,8-
dimethyl~iroj4H I-
benzothiopyran-4.2'-[1,3]dioxolane]-6-carboxylate 1,I-dioxide
3.0 g (9.6 mmol) of the title compound of Step F in Example i, 2.5 mL (0.029
mol)
of oxalyl chloride (purchased from Janssen), and 2 drops of N,N
dimethylformamide were
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18
added to 100 mL of methylene chloride;. The mixture was refluxed under
nitrogen for 2 h,
and was then evaporated to dryness. l00 mL of methylene chloride was added to
the residue
and evaporated to dryness. Another l00 mL of methylene chloride was added to
the residue,
and the solution was cooled to about 0 ~C. 1.19 g (0.0106 mol) of 1,3-
cyclohexanedione
(purchased from Aldrich Chemical Company) was added followed by 4.1 S mL
(0.030 mol)
of triethylamine, and the mixture was stirred overnight while warming to room
temperature.
The mixture was evaporated to dryness and the crude product was
chromatographed over
silica gel eluting with a mixture of ethyl acetate : hexane ( 1 : 1 ) to yield
1.33 g of the title
compound of Step A as a solid melting at 109-111 ~C. 1 H NMR (CDC13): 8 2. I
(m,2H), 2.5
(m,SH), 2.6 (m,2H), 2.? (m,2H), 2.8 (s,3H), 3.5 (m,2H), 4.2 (m,2H), 4.3
(m,2H), 6.0 (s,lH),
7.7 (s, l H).
Step B: Preparation of 2-((2,3-dihydro-5,8-dimethylspiro[4H 1-benzothiopyran-
4,2'-
I1.3]dioxolan]-6-yl)carbonyl]-1,3-cyclohexanedione S.S dioxide
l.33 g (3.3 mmol) of the title compound of Step A, 1 drop of acetone
cyanohydrin
(purchased from Aldrich Chemical Company), and 0.80 mL (5.7 mmol) of
triethylamine
were added to 50 mL of acetonitrile and the mixture was allowed to stir for
1.5 h. About
0.06 g of potassium cyanide was added to the mixture which was then stirred
overnight at
room temperature under nitrogen. Another 0.03 g of potassium cyanide was added
to the
mixtwe which was then stirred for 3 h. The mixture was then evaporated to
dryness, water
was added to the residue, and the aqueous mixture was acidified to pH 1 with
concentrated
hydrochloric acid and filtered. The solid residue was dissolved in methylene
chloride and
the resulting solution was dried (MgS04), filtered, and evaporated to dryness
to yield 1.09 g
of the title compound of Step B, a compound of the invention, as a solid
melting at 130 ~C
(dec.). 1H NMR (CDC13): 8 2.0 (m,2H), 2.2 (s,3H), 2.6 (m,6H), 2.7 (s,3H), 3.5
(m,2H),
4.14 (m,2H), 4.26 (m,2H), 6.9 ( 1 H).
Step C: Preparation of 2-[(2,3-dihydro-5,8-dimethvls iro(4H 1-benzothiopyran-
4,2'-
j 1,3ldioxolanl-6-yl)carbonyl]-1,3-cyclohexanedione S.S dioxide monolithium
salt
8.0 g of the title compound of Step B, 760 mg of lithium methoxide, and 560 mL
of
methanol were added to a flask and the resulting mixture was stirred at room
temperature for
3 days under a nitrogen atmosphere. The reaction mixture was then concentrated
under
reduced pressure and the residue was triturated with ether. The resulting
solid was collected
by filtration and dried under vacuum to yield 7.0 g of the title compound of
Step C, a
compound of this invention, as a solid melting at 266-267 ~C. ~ H NMR
((CD3)2S0): 8
3 5 1.75-1. 85 (m, 2H), 2.08 (s, 3 H), 2.2-2.3 5 (m, 4H), 2.4-2.6 (m, 5 H),
3.42-3 .54 (m, 2H), 4.05-
4.25 (m, 4H), 6.83 (s, 1 H).
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19
Example 3
St- ea A: f reparation of?-f(?.3-dihydro-5,8-dimethvlspiro~4H 1-benzothiopvran-
4.2'-
j 1,3ldioxolan]-6-yl)carbonylL 1,3-cvclohexanedione S S-dioxide
monopotassium salt
6.0 g of the title compound of Step B of Example 2, 1.06 g of potassium
methoxide,
and 420 mL of methanol were added to a flask and the resulting mixture was
stirred at room
temperature overnight under a nitrogen atmosphere. The reaction mixture was
then
concentrated under reduced pressure and the residue was triturated with ether.
The resulting
solid was collected by filtration, washed further with ether, and dried under
vacuum to yield
6.56 g of the title compound of Step A, a compound of this invention, as a
solid melting at
>215 ~C. tH NMR ((CD3)2S0): 8 1.65-1.78 (m, 2H), 2.0-2.15 (m, 7H), 2.4-2.53
(m, SH),
3.4-3.5 (m, 2H), 4.05-4.25 (m, 4H), 6.76 (s, 1 H).
Example 4
Step A: Preparation of 2-f(2,3-dihydro-5,8-dimethylst7iro14H 1-benzothiwran-
4,2'-
I S [I ,3Lioxolan]-6-~)carbonvlLl ,3-cvclohexanedione S. S dioxide monosodium
salt
580 mg of sodium metal was added to 700 mL of methanol and the reaction was
stirred at room temperature until the complete disappearance of the sodium
metal. To this
solution was added I0.0 g of the title compound of Step B of Example 2, and
the resulting
mixture was stirred at room temperature overnight under a nitrogen atmosphere.
The
reaction mixture was then concentrated under reduced pressure and the residue
was triturated
with ether. The resulting solid was collected by filtration, washed further
with ether, and
dried under vacuum to yield 10.5 g of the title compound of Step A, a compound
of this
invention, as a solid melting at >215 ~C. ~H NMR ((CD3)2S0): b I.67-1.8 (m,
2H), 2.0-2.2
(m, 7H), 2.4-2.57 (m, SH), 3.4-3.5 (m, 2H), 4.05-4.25 (m, 4H), b.76 (s, 1 H).
Example 5
Step A: Preparation of 2-f(2,3-dihydro-5,8-dimethvlspiro[4H I-benzothionyran-
4,2'-
Ll .3~dioxolan]-6-yl~carbonyl]-1,3-cyclohexanedione S..S-dioxide
benzvldimethylhexadecvlammonium salt
1.22 g of benzyldimethylhexadecylammonium chloride monohydrate was dissolved
in 3 mL of dichloromethane and then 3.3 mL of 1 N aqueous NaOH was added and
the
mixture was thoroughly stirred. In a separate vial, I .25 g of the title
compound of Step B of
Example 2 was dissolved in 3 mL of dichloromethane, and this solution was
added to the
contents of the previously prepared ammonium salt solution. After thorough
mixing, the
3 S mixture was transferred to a separatory funnel and the organic layer was
separated. The
aqueous layer was extracted three times with 3 mL portions of dichloromethane
and the
combined organic layers were washed with water and dried over molecular sieves
for 4
hours. The sieves were removed by filtration and the solution was concentrated
under
CA 02270245 1999-04-28
WO 98/28291 PCT/US97/23469
reduced pressure to provide the title compound of Step A, a compound of this
invention, as a
tan solid (45% yield).
By the procedures described herein together with methods known in the art) the
following compounds of Tables 1 and 2 can be prepared.
5
TABLE 1
F
M~
R6a
b
r
wherein r is l and
M is Li
R I R2 n R4 RS R6a R6b
C=O I H H H H
C=O 2 H H H H
C=O 1 H H H CH3
C=O 2 H H H CH3
C=O 1 H H GHg CH3
C=O 2 H H CH3 CH3
C=O 1 CHg H H H
C=O 2 CHg H H H
C=O 1 CH3 H H CH3
C=O 2 CH3 H H CH3
C=O 1 CH3 H CH3 CH3
C=O 2 CH3 H CH3 CH3
C=O 1 CH3 CH3 H H
C=O 2 CHg CH3 H H
C=O 1 CH3 CHI H CH3
C=O 2 CH3 CH3 H CH3
C=O 1 CH3 CH3 CH3 CH3
C=O 2 CH3 CH3 CH3 CH3
C=O 1 CI Cl H H
C=O 2 Cl Cl H H
C=O 1 Cl CI H CH3
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WO 98/28291 PCT/US97/23469
21
C=O 2 CI CI H CH3
C=O 1 C1 CI CH3 CH3
C=O 2 Cl CI CH3 CHI
-OCH~CH20- 0 H H H H
-OCH~CH~O- I . H H H H
-OCH~CH~O- 2 H H H H
-OCHZCH20- 0 H H H CH3
-OCH2CH20- l H H H CH3
-OCH~CH20- 2 H H H CH3
-OCH~CH20- 0 H H CHg CH3
-OCHZCH20- 1 H H CH3 CH3
-OCHZCH20- 2 H H CH3 CH3
-OCHZCH20- 0 CHg H H H
-OCH2CH2O- I CHg H H H
-OCH2CH20- 2 CH3 H H H
-OCH2CH20- 0 CH3 H H CH3
-OCH2CH20- 1 CH3 H H CH3
-OCH2CH20- 2 CH3 H H CH3
-OCH2CH20- 0 CH3 H CH3 CHg
-OCH2CHZ0- 1 CH3 H CH3 CH3
-OCH2CH20- 2 CH3 H CH3 CH3
-OCHZCH20- 0 CH3 CH3 H H
-OCH2CH20- 1 CH3 CH3 H H
-OCH2CHZ0- 2 CH3 CH3 H H
-OCH2CH20- 0 CH3 CH3 H CH3
-OCH2CH20- I CH3 CH3 H CH3
-OCH2CH20- 2 CH3 CH3 H CH3
-OCH2CH20- 0 CH3 CH3 CH3 CH3
-OCH2CH20- I CH3 CH3 CH3 CH3
-OCH2CH20- 2 CH3 CH3 CH3 CH3
-OCH2CH20- 0 CI Cl H H
-OCH2CH20- I CZ Cl H H
-OCH~CH20- 2 Cl CI H H
-OCHZCH20- 0 CI Cl H CH3
-OCHZCH20- I Cl CI H CH3
-OCH~CH~O- Z C1 Cl H CH3
-OCH2CH20- 0 Cl CI CH3 CH3
-OCH2CH20- I CI CI CH3 CH3
HO HJ IJ IJ Z -O(HJ)ZHJ(~HJ)ZHOO-
HJ ~HJ IJ IJ 1 -O(HJ)ZHJ(HJ)ZHJO-
~H~ ~HJ IJ IJ 0 -O(HJ)ZHJ(HJ)ZHJO-
HJ H IJ IJ Z -O(~HJ)ZHJ(~HJ)ZHJO-
H~ H IJ IJ I -O(HJ)ZHJ(HJ)ZHJO-
HJ H IJ iJ 0 -O(~HJ)ZHJ(HJ)~HJO-
H H tJ IJ Z -O(HJ)ZHJ(HJ)ZHJO-
H H IJ fJ I -O(H~)~HJUHJ)ZHJO-
H H IJ IJ 0 -O(H~)ZHJ(HJ)ZHJO-
HJ HJ ~HJ ~HJ Z -O(H~)ZHJ(~HJ)ZHJO-
HJ HJ HJ H~ I -O(H~)ZHJ(HJ)ZHOO-
H~ HJ Ha H~ 0 -O~H~)ZHJ(H~)ZH~O-
HJ H H~ H~ Z -O(~H~)ZH~(H~)ZH~O-
H~ H HJ ~H~ 1 -O(HO)ZHO(HJ)ZHJO-
HJ H ~HJ HO 0 -OOH~)ZHJ(HJ)ZHOO-
H H HJ HJ Z -O(HO)ZHJ(H~)ZHJO-
H H HJ HO I -O(HO)ZHO(HJ)ZHJO-
H H H~ H~ 0 -O(H~)ZHWHJ)ZHJO-
~H~ H~ H H1 Z -O(H~)ZH~(H~)ZHOO-
H~ H~ H N~ l -O(H~)ZH~(H~)ZHOO-
H~ H~ H H~ 0 -O(H~)ZHO(HJ)ZHOO-
HJ H H H~ Z -O~H~)ZHJ(~HJ)ZHJO-
HJ H H H~ i -O(HO)ZHJ(HJ)ZHJO-
H~ H H H~ 0 -O(~H~)ZH~(HJ)ZH~O-
H H H HJ Z -O(H~)ZH~(HJ)ZN~O-
H H H H~ I -O~HO)ZH~(H~)ZH~O-
H H H HJ 0 -O(H~)ZHJ(HJ)ZH~O-
~H~ HJ H H Z -O~HO)ZHJ(HJ)ZHJO-
~HJ H~ H H I -O(HJ)ZHJ(HJ)ZHJO-
HJ ~HJ H H 0 -O(~HJ)~HJ(HJ)~HJO-
HJ H H H Z -O(HJ)GHJ(HJ)~HJO-
HJ H H H 1 -O(HJ)~HJ(~HJ)ZHJO-
HJ H H H 0 -OOHJ)~HJ(~HJ)~HJO-
H H H H Z -O(HJ)ZHJ(~HJ)ZHJO-
H H H H 1 -O(HJ)~HJ('HJ)~HJO-
H H H H 0 -O(HJ)~HJ(~HJ)~HJO-
HJ ~HJ IJ IJ Z -O~HJ~HJO-
691b~Z/G6SfI/,LOd I6Z8Z/86 OM
8Z-b0-666l SbZOGZZO ~a
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WO 98/28291 PCT/US97/23469
ZJ
wherein r is 1 and M is
Na
R I R? n R4 R5 R6a R6b
C=O l H H H H
C=O ? H H H H
C=O 1 H H H CH3
C=0 2 H H H CH3
C=O 1 H H CH3 CH3
C=O 2 H H CH3 CH3
C=O I CH3 H H H
C=O 2 CH3 H H H
C=O 1 CH3 H H CH3
C=O 2 CH3 H H CH3
C=O 1 CH3 H CH3 CH3
C=O 2 CH3 H CH3 CHg
C=O 1 CHg CH3 H H
C=O 2 CHg CH3 H H
C=O 1 CH3 CH3 H CH3
C=O 2 CH3 CH3 H CHg
C=O 1 CH3 CH3 CH3 CH3
C=O 2 CH3 CH3 CH3 CH3
C=O 1 Cl Cl H H
C=O 2 Cl CI H H
C=O 1 Cl Cl H CH3
C=O 2 Cl Ci H CH3
C=O 1 Cl Cl CH3 CH3
C=O 2 Cl CI CH3 CH3
-OCH2CH20- 0 H H H H
-OCH2CH20- 1 H H H H
-OCH2CH20- 2 H H H H
-OCH2CH20- 0 H H H CH3
-OCH2CH20- l H H H CH3
-OCH2CH20- 2 H H H CH3
-OCH2CH~0- 0 H H CH3 CH3
-OCH2CH20- 1 H H CH3 CH3
-OCHZCH20- 2 H H CHI CH;
-OCH2CH20- 0 CH3 H H H
-OCHZCH~O- 1 CH3 H H H
-OCHZCH20- 2 CH3 H H H
HO H H H~ l -O(H~)ZH~(H~)ZH~O-
HO H H ~H~ 0 -O(H~)ZHO(H~)ZH~O-
H H H H~ Z -O(H~)ZH~(H~)~H~O-
H H H H~ I -O(H~)ZH~(H~)ZH~O-
H H H HO 0 -O(HO)ZH~(H~)ZH~O-
H~ H~ H H Z -O(H~)ZH~(H~)ZH~O-
HO H~ H H I -O(H~)ZH~(H~)ZN~O-
HO H~ H H 0 -O(H~)ZHO(H~)ZH~O-
H~ H H H Z -O(H~)ZH~(H~)ZHaO-
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HO H~ H HO 0 -O(HO)ZHJ(H~)ZH~O-
HO H H HO Z -OtHO)ZHOtHJ)ZHJO-
H~ H H H~ I -O(H~)ZH~(HJ)ZHJO-
~HJ H H HO 0 -O(HO)ZHJ(HJ)ZHJO-
H H H HO Z -O(HO)ZHJ(HJ)ZHJO-
H H H H~ I -OtHO)ZHJ(H~)ZHJO-
H H H H~ 0 -O(HO)ZHO(H~)ZHJO-
HJ HJ H H Z -O(Ha)ZHO(HJ)ZHJO-
HJ HJ H H l -O(H~)ZHJ(HJ)ZHJO-
HJ HJ H H 0 -O(HJ)ZHJ(HJ)ZHJO-
HJ H H H Z -O(HJ)ZHJ(HJ)~HJO-
HJ H H H I -O(HJ)ZHJ(~HJ)~HJO-
HJ H H H 0 -O(HJ)~HJ(HJ)~HJO-
H H H H Z -O(HJ)ZHJ('HJ)LHJO-
H H H H l -O(HJ)ZHJ('HJ)~HJO-
H H H H 0 -O(HJ)~HJ(~HJ)~HJO-
~HJ ~HJ IJ IJ c -O~HJ~HJO-
HJ ~HJ IJ (J I -O~HJ~HJO-
C
69V~Z/L,6Sl1/.LOd T6Z8Z/86 OM
SZ-b0-666i SbZOLZZO ~Ta
CA 02270245 1999-04-28
WO 98/28291 PCTlUS97/23469
36
wherein r is 1 and M is (CH3~N
R' n R4 R~ f26a R6b
C=p I H H H H
C=O 3 H H H H
C=O 1 H H H CH3
C=O 2 H H H CH3
C=O 1 H H CHI CH3
C=O 2 H H CH3 CH3
C=O 1 CH3 H H H
C=O 2 CH3 H H H
C=O I CH3 H H CH3
C=O 2 CH3 H H. CH3
C=O 1 CH3 H CH3 CH3
C=O 2 CH3 H CH3 CH3
C=O 1 CH3 CH3 H H
C=O 2 CH3 CH3 H H
C=O I CH3 CH3 H CH3
C=O 2 CH3 GH3 H CH3
C=O I CH3 CH3 CH3 CH3
C=O 2 CH3 CH3 CH3 CH3
C=O I CI CI H H
C=O 2 Cl Cl H H
C=O 1 Cl CI H CH3
C=O 2 Cl CI H CH3
C=O I CI Cl CH3 CH3
C=O 2 Cl Cl CH3 CH3
-OCH2CH20- 0 H H H H
-OCH2CH20- 1 H H H H
-OCH2CH20- 2 H H N H
-OCH2CH20- 0 H H H CH3
-OCH2CH20- I H H H CH3
-OCH~CH~O- 2 H H H CH3
-OGH~CH20- 0 H H CH3 CHI
-OCH~CH20- 1 H H CH3 CH3
-OCHZCH20- 2 H H CH3 CH3
-OCH2CH~0- 0 CH3 H H H
-OCH~CH20- 1 CHI H H H
H~ H H H~ 0 -O(HO)ZH~(H~)~H~O-
H H H H~ Z -O(H~)ZH~(H~)ZH~O-
H H H H~ t -O(H~)ZH~(~H~)ZH~O-
H H H H~ 0 -O(H~)ZH~(H~)ZH~O-
H~ H~ H H Z -O(HO)ZH~(H~)ZH~O-
H~ H~ H H 1 -O~H~)ZH~UH~)ZH~O-
H~ H~ H H 0 -O(~HO)~H~(H~)ZH~O-
H~ H H H Z -O~H~)ZH~(H~)ZH~O-
H~ H H H 1 -O(HO)ZH~(H~)ZH~O-
H~ H H H 0 -O(H~)ZH~(H~)ZH~O-
H H H H Z -O(HO)ZH~(H~)ZH~O-
H H H H I -O(H~)ZH~(~H~)ZH~O-
H H H H 0 -O~H~)ZH~(HO)ZHOO-
H~ H~ 1~ I~ Z -OZH~ZHOO-
H~ ~H~ l~ I~ I -OZH~ZH~O-
H~ H~ 10 I~ 0 -OZH~ZH~O-
H~ H I~ I~ Z -OZH~ZHOO-
~H~ H i~ l~ I -OZH~ZHOO-
H~ H to I~ 0 -OZH~ZHOO-
H H t~ I~ Z -OZH~ZHOO-
H H l~ f0 I -OZH~ZH~O-
H H I~ l~ 0 -OZH~ZH~O-
H~ H~ ~H~ H~ Z -OZH~ZH~O-
~H~ H~ H~ H~ I -OZH~ZHOO-
~H~ H~ H~ H~ 0 -OZN~ZH~O-
~H~ H H~ H~ Z -OZH~ZH~O-
H~ H H~ ~H~ I -OZH~ZH~O-
H~ H H~ H~ 0 -OZH~~H00-
H H H~ H~ Z -OZH~~H~O-
H H H~ H~ I -OZHaZH~O-
H H ~H~ ~H~ 0 -O~H~~H~O-
H~ ~H~ H ~H~ Z -OZH~~H~O-
H~ LH~ H H~ l -O~H~~H~O-
~H~ ~H~ H ~H~ 0 -O~H~~H~O-
H~ H H ~H~ Z -O~H~~H~O-
~H~ H H H~ I -O~HJ~HJO-
'H~ H H HJ 0 -OZHJ~H~O-
H H H H~ Z -O~H~~H~O-
L~
69b~Z/G6SIlI,L~d T6ZSZ/86 OM
8Z-b0-666l SbZOLZZO ~a
HJ HJ H HJ Z O=J
H~ 'HJ H HJ I O=J
~HJ H H HJ Z O=J
HJ H H HJ I O=J
H H H HJ Z O=J
H H H HJ I O=J
HJ ~HJ H H Z O=J
HJ HJ H H I O=J
HJ H H H Z O=J
HJ H H H I O=J
H H H H Z O=J
H H H H I O=J
99~ E9~ S~ ti~ a Z~ I ~
~zH~SH9~z~~H~~~H9I~ st y~ ptt~ I st .z uta.taunn
HJ HJ IJ f0 Z -O(HO)ZHa(H~)ZHJO-
H~ HJ 1J IJ I -O(H~)ZHJ(H~)ZHJO-
H~ HJ IJ 10 0 -O(H~)ZHJ(~HO)ZHJO-
H~ H I~ IO Z -O(HO)ZHJ(H~)ZHJO-
HJ H I~ IO I -O(HO)ZHO(H~)ZHOO-
H~ H 10 IJ 0 -O(HO)ZHJ(HJ)ZHJO-
H H IJ I~ Z -O(HO)ZHJ(HJ)ZHJO-
H H 1J IJ I -O(H~)ZHJ(HJ)ZHJO-
H H IJ f0 0 -O(HO)ZHJ(HO)ZHOO-
H~ HJ HJ HJ Z -O(HO)ZHJ(HO)ZH~O-
HJ HJ ~HJ HO I -O(HO)ZH~(H~)ZHOO-
H~ HJ HJ HO 0 -O(H~)ZHO(H~)ZHOO-
HJ H HJ HO Z -O(H~)ZHJ(HJ)ZHJO-
HJ H HJ HJ I -O(HJ)ZHJ(H~)ZHJO-
HJ H HJ HJ 0 -O(HJ)ZHJ(HJ)ZHJO-
H H HJ HJ Z -O(HJ)ZHJ(HJ)ZHJO-
H H HJ ~HJ 1 -O(~HJ)ZHJ(HJ)GHJO-
H H HJ HJ 0 -O(HJ)ZHJOHJ)ZHJO-
HJ HJ H ~HJ Z -O(HO)~HJ(EHJ)~HJO-
LHJ ~HJ H ~HJ I -O(HJ)ZHJ(~HJ)~HJO-
'HJ ~HJ H ~HJ 0 -O(HJ)~HJ(~HJ)~HJO-
'HJ H H ~HJ v -O(~HJ)~HJ(~HJ)~HJO-
~HJ H H yHJ I -O(HJ)~HJ(~HJ)~HJO-
8c
691d~Z/46Sf1l,ILOd i6Z8Z/86 OM
8Z-b0-666l SbZOGZZO ~a
CA 02270245 1999-04-28
WO 98/28291 PCT/US97/23469
39
C=O t CHI CH3 H H
C=O 2 CH3 CHI H H
C=O 1 CHI CHI H CHI
C=O 2 CHI CH; H CHI
C=O 1 CHI CH3 CH3 CH3
C=O 2 CHI CHI CH3 CH3
C=O i CI CI H H
C=O 2 CI Cl H H
C=p 1 CI Cl H CH3
C=O 2 Cl CI H CH3
C=O l Cl Cl CH3 CHg
C=O 2 Cl CI CHg CH3
-OCH2CH20- 0 H H H H
-OCH2CH20- 1 H H H H
-OCH2CH20- 2 H H H H
-OCH2CH20- 0 H H H CH3
-OCH2CH20- 1 H H H CH3
-OCH2CH20- 2 H H H CH3
-OCH2CH20- 0 H H CH3 CH3
-OCHZCH20- 1 H H CH3 CH3
-OCH2CH20- 2 H H CH3 CH3
-OCH2CHZ0- 0 CH3 H H H
-OCH2CH20- I CH3 H H H
-OCH2CH20- 2 CH3 H H H
-OCH2CH20- 0 CH3 H H CH3
-OCH2CH20- 1 CHg H H CN3
-OCH2CH20- 2 CH3 H H CH3
-OCH2CH20- 0 CH3 H CH3 CH3
-OCH2CH20- t CH3 H CH3 CH3
-OCHZCH20- 2 CH3 H CH3 CH3
-OCH2CH20- 0 CH3 CH3 H H
-OCH2CH20- I CH3 CH3 H H
-OCH2CH~0- 2 GH3 CH3 H H
-OCH2CHZ0- 0 CH3 CH3 H CH3
-OCH2CH20- 1 CH3 CH3 H CH3
-OCH2CH20- 2 CH3 GHQ H CHI
-OCH2CH~0- 0 CH3 CH3 CH3 CH3
-OCH~CH20- 1 CHg CH3 CH3 CHg
H H IJ 1J 0 -O(HJ)ZHJ(HJ)ZHJO-
~HJ HJ ~HJ HJ Z -OOHJ)~HJ(HJ)~HJO-
HJ HJ ~HJ H~ I -O(HJ)ZHJ(HJ)ZHJO-
~HJ ~HJ HJ HJ 0 -O(HJ)ZHJ(HJ)ZHJO-
HJ H HJ HJ Z -O(HJ)ZHJ(HJ)ZHJO-
HJ H yHJ H~ 1 -O(HJ)ZHJ(HJ)ZHJO-
HJ H ~HJ HJ 0 -O(~HJ)ZHJ(HJ)ZHJO-
H H ~HJ H~ Z -O(HJ)ZHJ(HJ)ZHJO-
H H ~HJ HJ I -O(H~)ZHJ(HJ)ZHJO-
H H HJ HJ 0 -O(HO)ZHJ(HJ)ZHJO-
HJ FHJ H H~ Z -O(HJ)ZHJ(HJ)ZHJO-
HJ HJ H HJ I -O(HJ)ZHJ(HJ)ZHJO-
HJ HJ H ~HJ 0 -O~H~)ZHJ~HJ)ZHJO-
HJ H H HJ Z -O(HJ)ZHJ(HJ)ZHOO-
~HJ H H EHJ I -O~HO)ZHJ(HJ)ZHJO-
HJ H H HJ 0 -OOH~)ZHJ(HO)ZHOO-
H H H HJ Z -O(Ha)ZHJ(~HJ)ZHJO-
H H H HJ I -O(~HJ)ZHJ(HJ)ZHJO-
H H H H~ 0 -O(H~)ZHJ(HJ)ZHJO-
HJ HJ H H Z -O(H~)ZHJ~HJ)ZH~O-
HJ H~ H H I -O~H~)ZHJ(HJ)ZHOO-
HJ H~ H H 0 -O(HJ)ZHJ(HJ)ZHOO-
~HJ H H H Z -O~HJ)ZHJ(HJ)ZHJO-
HJ H H H I -OtHJ)ZHJ(HJ)ZHJO-
HJ H H H 0 -OtHJ)ZHJ(HJ)ZHOO-
H H H H Z -O(HJ)ZHJ(HJ)ZHOO-
H H H H t -O~H~)ZHJ(HO)ZHOO-
H H H H 0 -O~HJ)ZHJ(HJ)ZHOO-
HJ HJ IJ IJ Z -OZHJZHJO-
~HJ H~ 1J lJ t -OZHJZHJO-
HJ HJ IJ IJ 0 -O~HJZHJO-
HJ H !J IJ Z -O~HJ~HJO-
'HJ H 1J IJ t -OLHJ~HJO-
~HJ H IJ IJ 0 -O~HJ~HJO-
H H IJ IJ Z -O~HJ~HJO-
H H IJ IJ l -O~HJ~HJO-
H H IJ IJ 0 -O~HJ~HJO-
~HJ ~HJ ~HJ ~HJ i. -O~HJ~HJO-
Ob
69fi~Z/G6SIILLOd I6Z8Z/86 OM
8Z-b0-6661 SbZOLZZO ~a
H H H H Z -O~H~ZH~O-
H H H H I -O~H~ZH~O-
H H H H 0 -OZH~ZH~O-
H~ H~ I~ l~ Z O=~
H~ H~ I~ I~ 1 O=~
H~ H 1~ I~ Z O=O
~H~ H 1~ l~ I O=~
H H I~ (O Z O=~
H H I~ I~ I O=~
H~ ~H~ MHO H~ Z O=~
H~ ~H~ H~ H~ i O=~
H~ H H~ H~ Z O=~
HO H H~ HO I O=~
H H H~ HO Z O=O
H H N~ H~ 1 O=~
HO H~ H ~H~ Z O=~
H~ H~ H H~ I O---~
H~ H H fH~ Z O=~
HO H H HO I O=O
H H H H~ Z O=O
H H H HO I O=~
H~ H~ H H Z O=~
H~ H~ H H I O=~
H~ H H H Z O=O
HO H H H I O=~
H H H H Z O=~
H H H H I O=~
99~ E9~ S~ b~ a Z~ I ~
o~ sc y~ pue Z st .~ uia.~aqnn
~H~ ~H~ l~ I~ Z -O(H~)ZH~(H~)~H~O-
~H~ ~H~ f~ I~ I -O(H~)ZH~(EH~)ZHJO-
~HO ~H~ l~ l~ 0 -O(EH~)~HO(HO)~H~O-
~H~ H l~ I~ Z -O(~H~)~H~(~H~)~H~O- .
H~ H l~ l~ l -O(H~)ZH~(H~)~H~O-
~H~ H IJ i~ 0 -O(H~)~H~(H~)~H~O-
H H I~ l~ Z -O(~H~)~HJ(HJ)~H~O-
W H I~ i~ I -O(H~)ZH~(~H~)~H~O-
lb
69t~~ZIG6SIIl,L,~d I6Z8Z/86 OM
8Z-b0-666l SbZOGZZO ~a
HO 'HJ IJ !J Z -OZHJ~HJO-
HJ HJ IJ lJ 1 -OZHJZHJO-
HJ HJ IJ IJ 0 -OZHJZHJO-
H~ H IJ IJ Z -OZHJ~HJO-
H~ H IJ IJ t -OZHJ~HJO-
H~ H IJ IJ 0 -OZHJ~HJO-
H H lJ IJ Z -OZH~ZHJO-
H H IJ I~ t -OZH~~H~O-
H H IJ I~ 0 -OZHOZH~O-
HO H~ HJ H~ Z -OZHJZHOO-
HO H~ HJ H~ i -OZHJZHJO-
HO H~ H~ H~ 0 -OZH~ZHJO-
H~ H HJ HJ Z -OZHJZHJO-
~HO H HJ HJ I -OZH~zHJO-
HO H H~ H~ 0 -OZHaZH~O-
H H HO H~ Z -OZH~ZH~O-
H H HO Ha I -OZH~ZH~O-
H H HO H~ 0 -OZHJZHJO-
HO HJ H H~ Z -OZHJZHJO-
EHO H~ H Ha t -OZH~ZH~O-
~HO ~H~ H HJ 0 -OZH~ZHaO-
H~ H H H~ Z -OZH~ZHJO-
I-I~ H H H~ t -OZH~ZHJO-
~H~ H H HJ 0 ~OZHJ~H~O-
H H H HJ Z -OZHJ~HJO-
H H H HJ I -OZHJZHJO-
H H H HJ 0 -OZHJ~HJO-
H~ ~HJ H H Z -O~HJ~HJO-
~HJ HJ H H I -O~HJLHaO-
~HJ ~HJ H H 0 -O~HJ~HJO-
~HJ H H H Z -O~HJ~HJO-
~HJ H H H I -O~HJ~HJO-
~HJ H li H 0 -O~HJ~HJO-
G~
69b~Z/G6SI1/,LOd i6Z8Z186 OM
SZ-b0-666l SbZOLZZO ~'a
CA 02270245 1999-04-28
WO 98/28291 PCT/US97/23469
43
wherein r is 2 and M is Ni
I R2 R R4 RS Rba R6b
n
C=O I H H H H
C=O 2 H H H H
C=O 1 H H H CHI
C=O 2 H H H CHI
C=O I H H CH3 CHI
C=O 2 H H CH3 CH3
C~O I CH3 H H H
C=O 2 CH3 H H H
C=O 1 CH3 H H CHg
C=O 2 CH3 H H CH3
C=O I CH3 H CH3 CH3
C=O 2 CH3 H CH3 CH3
C=O I CH3 CH3 H H
C=O 2 CH3 CHg H H
C=O 1 CH3 CH3 H CH3
C=O 2 CH3 CH3 H CH3
C=O 1 CHg CH3 CH3 CH3
C=p 2 CH3 CH3 CH3 CH3
C=O I C1 Cl H H
C=O 2 Cl CI H H
C=O I CI Cl H CH3
C=O 2 Cl C1 H CH3
C=O I C1 Cl CHg CH3
C=O 2 CI Cl CH3 CH3
-OCH2CH20- 0 H H H H
-OCH2CH20- I H H H H
-OCH2CH20- 2 H H H H
-OCH2CH20- 0 H H H CH3
-OCH2CH20- I H H H CH3
-OCH2CH20- 2 H H H CH3
-OCH2CH20- 0 H H CH3 CH3
-OCH2CH20- 1 H H CH3 CH3
-OCH2CH20- 2 H H CH3 CH3
-OCHZCH20- 0 CH3 H H H
-OCH2CH20- 1 CH3 H H H
-OCH2CH20- ? CH3 H H H
CA 02270245 1999-04-28
WO 98/28291 PCT/US9~/23469
4~1
-OCH~CH~O- 0 CHI H H CHI
-OCH~CH~O- I CHI H H CHI
-OCH~CH~O- '- CH; H H CH3
-OCH~CH~O- 0 CHI H CH3 CH3
-OCH~CH20- 1 CHI H CH3 CH3
-OCH2CH~0- 2 CH3 H CH3 CH3
-OCH2CH20- 0 CH3 CH3 H H
-OCH2CH20- t CH3 CH3 H H
-OCH2CH20- 2 CH3 CH3 H H
-OCH2CH20- 0 CH3 CHI H CH3
-OCH2CH20- 1 CH3 CH3 H CHg
-OCH2CH20- 2 CH3 CH3 H CH3
-OCH2CH20- 0 CH3 CH3 CH3 CH3
-OCH2CH20- 1 CH3 CH3 CH3 CH3
-OCH2CH20- 2 CH3 CH3 CH3 CH3
-OCH2CH2O- 0 CI Cl H H
-OCH2CH20- 1 Cl Cl H H
-OCH2CH20- 2 Cl CI H H
-OCH2CH20- 0 CI Cl H CH3
-OCH2CH20- 1 Cl Cl H CH3
-OCH2CH20- 2 Cl CI H CH3
-OCH2CH20- 0 Cl Cl CH3 CH3
-OCH2CH20- 1 Cl C1 CH3 CH3
-OCH2CH20- 2 CI Cl CH3 CH3
wherein r is 2 and M is Cu
R I RZ n R'~ RS R6a
C=O 1 H H H H
C=O 2 H H H H
C=O 1 H H H CH3
C=O 2 H H H CH3
C=O 1 H H CH3 CH3
C=O 2 H H CH3 CH3
C=O t CH3 H H H
C=O 2 CH3 H H H
C=O 1 CH3 H H CH3
C=O 2 CH3 H H CH3
C=O 1 CH3 H CH3 CH3
CA 02270245 1999-04-28
WO 98I28291 PCTlUS97l23469
C=O ? CHI H CHI CH3
C=O 1 CHI CHI H H
C=O 2 CH; CHI H H
C=O 1 CH3 CHI H CHI
C=O 2 CHI CHI H CHI
C=O f CHI CHI CHa CH3
C=O 2 CHI CHI CHI CH3
C=O 1 CI CI H H
C=O 2 CI CI H H
C=O 1 CI Cl H CH3
C=O 2 CI Cl H CH3
C=O 1 Cl Cl CH3 CHg
C=O 2 CI CI CH3 CH3
-OCH2CH20- 0 H H H H
-OCH2CH20- 1 H H H H
-OCH2CH20- 2 H H H H
-OCH2CH20- 0 H H H CH3
-OCH2CH20- 1 H H H CHg
-OCH2CH20- 2 H H H CH3
-OCH2CH20- 0 H H CH3 CH3
-OCH2CH20- 1 H H CH3 CH3
-OCH2CH20- 2 H H CH3 CH3
-OCH2CH20- 0 CHg H H H
-OCH2CH20- 1 CH3 H H H
-OCH2CH20- 2 CH3 H H H
-OCH2CH20- 0 CH3 H H CH3
-OCH2CH20- 1 CH3 H H CH3
-OCHZCH20- 2 CHg H H CH3
-OCH2CH20- 0 CH3 H CH3 CH3
-OCH2CH20- l CH3 H CH3 CH3
-OCH2CH20- 2 CH3 H CH3 CH3
-OCH~CH20- 0 CH3 CHg H H
-OCH2CH20- 1 CH3 CH3 H H
-OCH~CHZO- 2 CH3 CH3 H H
-OCH~CH20- 0 CH3 CH3 H CH3
-OCH~CH20- t CH3 CH3 H CH3
-OCH~CH20- 2 CH3 CH3 H CH3
-OCH~CH20- 0 CHg CH3 CH3 CH3
CA 02270245 1999-04-28
WO 98/28Z91 PCT/US97/23469
46
-OCH~CHZO- 1 CH3 CH3 CHI CH;
-OCH~CH~O- 3 CH3 CHI CH3 CHI
-OCH~CH~O- 0 CI CI H H
-OCH~CH~O- 1 CI CI H H
-OCH~CH20- 2 CI CI H H
-OCHZCH20- 0 CI Cl H CHI
-OCH~CH20- 1 CI CI H CH3
-OCH2CH20- 2 Cl CI H CH3
-OCH2CH20- 0 C1 CI CH3 CH3
-OCH2CH20- I C1 C1 CH3 CH3
-OCH2CH20- 2 CI Cl CH3 CH3
wherein r is 2 and
M is Zn
RI R n R4 RS R6a R6b
Z
C=O 1 H H H H
C=O 2 H H H H
C=O 1 H H H CH3
C=O 2 H H H CH3
C=O 1 H H CH3 CH3
C=O 2 H H CHg CH3
C=O 1 CH3 H H H
C=O 2 CH3 H H H
C=O 1 CH3 H H CH3
C=O 2 CH3 H H CH3
C=O I CH3 H CH3 CH3
C=O 2 CH3 H CH3 CH3
C=O 1 CH3 CHI H H
C=O 2 CHI CHI H H
C=O 1 CH3 CH3 H CH3
C=O 2 CH3 CH3 H CH3
C=O 1 CH3 CH3 CH3 CH3
C=O 2 CH3 CH3 CH3 CH3
C=O 1 Cl Ci H H
C=O 2 Ci Cl H H
C=O 1 CI Cl H CH3
C=O 2 CI Cl H CH3
C=O 1 CI C1 CH3 CH3
C=O 2 Cl Cl CH3 CH3
CA 02270245 1999-04-28
WO 98/28291 PCTIUS97i23469
47
-OCH~CH~O- 0 H H EI H
-OCH~CH~O- 1 H H H I-I
-OCH~CH~O- ? H H H H
-OCH~CH~O- 0 H H H CH3
-OCH~CH~O- 1 H H H CH3
-OCH~CH20- 2 H H H CH3
-OCH~CH20- 0 H H CHI CH3
-OCH?CH20- I H H CH3 CH3
-OCH2CH20- 2 H H CH3 CH3
-OCH~CH20- 0 CH3 H H H
-OCH2CH20- I CH3 H H H
-OCH2CH20- 2 CH3 H H H
-OCH2CH20- 0 CH3 H H CH3
-OCH2CH20- 1 CHg H H CH3
-OCH~CH20- 2 CH3 H H CH3
-OCH2CH~0- 0 CH3 H CH3 CH3
-OCHZCH20- 1 CH3 H CH3 CH3
-OCHZCH20- 2 CH3 H CH3 CH3
-OCH2CH20- 0 CH3 CH3 H H
-OCH2CH20- 1 CH3 CH3 H H
-OCH2CH20- 2 CH3 CHg H H
-OCH~CH20- 0 CH3 CH3 H CHI
-OCH2CH20- 1 CH3 CH3 H CH3
-OCHZCH20- 2 CH3 CH3 H CH3
-OCH2CH20- 0 CH3 CH3 CH3 CH3
-OCH2CH20- 1 CH3 CH3 CH3 CH3
-OCH2CH~0- 2 CH3 CH3 CH3 CH3
-OCH2CH~0- 0 CI C! H H
-OCH2CH20- I CI CI H H
-OCH2CH20- 2 CI CI H H
-OCH~CHZO- 0 CI CI H CH3
-OCH2CH20- 1 Cl Cl H CH3
-OCH~CH20- 2 CI Cl H CH3
-OCH~CH20- 0 CI Cl CHI CH3
-OCH~CH20- I CI Cl CH3 CH3
-OCH~CH~O- 2 Cl Cl CH3 CH3
H H~ Z -OUHO)zH~(HO)ZHOO-H ~HO Z -O(H~)ZH~(HO)ZH~O-
H ~H~ 1 -O(H~)ZH~(H~)ZH~O-H HO 1 -O(H~)ZH~(H~)ZH~O-
H ~H~ 0 -O(H~)ZH~(H~)ZH~O-H HO 0 -O(~H~)~H~(H~)ZHOO-
H H Z -O(EH~)ZH~(HO)ZH~O-H H Z -O(HO)ZH~(HO)ZHOO-
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CA 02270245 1999-04-28
WO 98/28291 PCT/US97/234b9
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Formulation/LJtility
Compounds of this invention will generally be used as a formulation or
composition
with an agriculturally suitable carrier comprising at least one of a liquid
diluent, a solid
S diluent or a surfactant. The formulation or composition ingredients are
selected to be
consistent with the physical properties of the active ingredient, mode of
application and
environmental factors such as soil type, moisture and temperature. Useful
formulations
include liquids such as solutions {including emulsifiable concentrates),
suspensions,
emulsions (including microemulsions and/or suspoemulsions) and the like which
optionally
can be thickened into gels. Useful formulations further include solids such as
dusts,
powders, granules, pellets, tablets, films, and the like which can be water-
dispersible
("wettable") or water-soluble. Active ingredient can be (micro)encapsulated
and further
formed into a suspension or solid formulation; alternatively the entire
formulation of active
ingredient can be encapsulated (or "overcoated"). Encapsulation can control or
delay release
of the active ingredient. Sprayable formulations can be extended in suitable
media and used
at spray volumes from about one to several hundred liters per hectare. High-
strength
compositions are primarily used as intermediates for further formulation.
The formulations will typically contain effective amounts of active
ingredient, diluent
and surfactant within the following approximate ranges which add up to 100
percent by
weight.
Weight Percent
Active
tneredientDiluent Surfactant
Water-Dispersible and 5-90 0-94 I-Z5
Water-soluble
Granules, Tablets and
Powders.
Suspensions, Emulsions,5-50 40-95 0-15
Solutions
(including Emulsifiable
Concentrates)
Dusts 1-25 70-99 0-S
Granules and Pellets 0.0l-99 5-99.99 0-15
High Strength Compositions 90-99 0-l0 0-2
CA 02270245 1999-04-28
WO 98/28291 PCT/US97/23469
54
Typical solid diluents are described in Watkins, et al., Handbook of
Insecticide Dust
Diltrc~nt.s and C'crrrle~r.s, 2nd Ed.. Dorland Books. Caldwell, New Jersey.
Typical liquid
diluents are described in Nlarsden, Solvents Guide, 2nd Ed., Interscience, New
York, 19S0.
~LlcCutcheon '.s Detergents crud Emtrlsifiers Annual, Allured Publ. Corp.,
Ridgewood, New
Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents,
Chemical Publ.
Co., Inc., New York, 1964, list surfactants and recommended uses. All
formulations can
contain minor amounts of additives to reduce foam, caking, corrosion,
microbiological
growth and the like, or thickeners to increase viscosity.
Surfactants include, for example, polyethoxylated alcohols, polyethoxylated
alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl
sulfosuccinates, alkyl
sulfates, alkylbenzene sulfonates, organosilicones, N,N dialkyltaurates,
lignin sulfonates,
naphthalene sulfonate formaldehyde condensates, polycarboxylates, and
polyoxyethylene/polyoxypropylene block copolymers. Solid diluents include, for
example,
clays such as bentonite, montmorillonite, attapulgite and kaolin, starch,
sugar, silica, talc,
1 S diatomaceous earth, urea, calcium carbonate, sodium carbonate and
bicarbonate, and sodium
sulfate. Liquid diluents include, for example, water, N,N dimethylformamide,
dimethyl
sulfoxide, N alkylpyrrolidone, ethylene glycol, polypropylene glycol,
paraffins,
alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, tong,
sesame, corn, peanut,
cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such
as
cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, and
alcohols
such as methanol, cyclohexanol, decanol and tetrahydrofurfuryl alcohol.
Solutions, including emulsifiable concentrates, can be prepared by simply
mixing the
ingredients. Dusts and powders can be prepared by blending and, usually,
grinding as in a
hammer mill or fluid-energy mill. Suspensions are usually prepared by wet-
milling; see, for
example, U.S. 3,060,084. Granules and pellets can be prepared by spraying the
active
material upon preformed granular carriers or by agglomeration techniques. See
Browning,
"Agglomeration", Chemical Engineering, December 4, 1967, pp 147-48, Perry's
Chemical
Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and
following,
and WO 91 / 13 546. Pel lets can be prepared as described in U. S. 4,172,7 l
4.
Water-dispersible and water-soluble granules can be prepared as taught in U.S.
4,144,050,
U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S.
5,180,587, U.S.
5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558
and U.S.
3,299,566.
For further information regarding the art of formulation, see U.S. 3,235,36l,
Col. 6,
line 16 through Col. 7, line 19 and Examples 10-41; U.S. 3,309,192, Col. 5,
line 43 through
Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, l32, 138-140, 162-
164, l66, 167
and 169-182; U.S. 2,89l,855, Col. 3, line 66 through Col. 5, line 17 and
Examples 1-4;
Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York,
1961,
CA 02270245 1999-04-28
WO 98I28291 PCT/US97/23469
pp 8l-96: and Hance et al., Weed Control Handbook) 8th Ed., Blackwell
Scientific
Publications. Oxford, 1989.
In the following Examples, all percentages are by weight and a11 formulations
are
prepared in conventional ways. Compound numbers refer to compounds in Index
Tables A-C.
Example A
High Strength Concentrate
Compound 3 98.5%
silica aerogel 0.5%
10 synthetic amorphous fine silica 1.0%.
Example B
Wettable Powder
Compound 4 65.0%
dodecylphenol polyethylene glycol ether 2.0%
15 sodium ligninsulfonate 4.0%
sodium silicoaluminate 6.0%
montmorillonite (calcined) 23.0%.
Example C
C'Tranule
20 Compound 10 10.0%
attapulgite granules (low volatile matter,
0.71i0.30 mm; U.S.S. No. 25-50 sieves) 90.0%.
Example D
Extruded Pellet
25 Compound 11 25.0%
anhydrous sodium sulfate 10.0%
crude calcium ligninsulfonate 5.0%
sodium alkylnaphthalenesulfonate 1.0%
calcium/magnesium bentonite 59.0%.
30 Test results indicate that the compounds of the present invention are
highly active
preemergent and postemergent herbicides or plant growth regulants. Many of
them have
utility for broad-spectrum pre- and/or postemergence weed control in areas
where complete
control of all vegetation is desired such as around fuel storage tanks,
industrial storage areas,
parking lots, drive-in theaters, air fields, river banks, irrigation and other
waterways, around
35 billboards and highway and railroad structures. Some of the compounds are
useful for the
control of selected grass and broadleaf weeds with tolerance to important
agronomic crops
which include but are not limited to alfalfa, barley, cotton, wheat, rape,
sugar beets, corn
(maize), sorghum, soybeans, rice, oats, peanuts, vegetables, tomato, potato,
perennial
CA 02270245 1999-04-28
WO 98/28291 PCT/US97/23469
~6
plantation crops including coffee, cocoa, oil palm, rubber, sugarcane, citrus,
grapes, fruit
trees, nut trees, banana, plantain, pineapple, hops, tea and forests such as
eucalyptus and
conifers (e.c., loblolly pine), and turf species (e.g., Kentucky bluegrass,
St. Augustine grass,
Kentucky fescue and Bermuda grass). Those skilled in the art will appreciate
that not all
compounds are equally effective against all weeds. Alternatively, the subject
compounds are
useful to modify plant growth.
A herbicidally effective amount of the compounds of this invention is
determined by a
number of factors. These factors include: formulation selected, method of
application,
amount and type of vegetation present, growing conditions, etc. In general, a
herbicidally
effective amount of compounds of this invention is 0.00l to 20 kg/ha with a
preferred range
of 0.004 to I .0 kglha. One skilled in the art can easily determine the
herbicidally effective
amount necessary for the desired level of weed control.
Compounds of this invention can be used alone or in combination with other
commercial herbicides, insecticides or fungicides. Compounds of this invention
can also be
1 S used in combination with commercial herbicide safeners such as benoxacor,
dichlormid and
furilazole to increase safety to certain crops. A mixture of one or more of
the following
herbicides with a compound of this invention may be particularly useful for
weed control:
acetochlor, acifluorfen and its sodium salt, aclonifen, acrolein (2-propenal),
alachlor,
ametryn, amidosulfuron, amitrole, ammonium sulfamate, anilofos, asulam,
atrazine,
azafenidin, azimsulfuron, benazolin, benazolin-ethyl, benfluralin,
benfuresate,
bensulfuron-methyl, bensulide, bentazone, bifenox, bispyribac and its sodium
salt, bromacil,
bromoxynil, bromoxynil octanoate, butachlor, butralin, butroxydim (ICIA0500},
butylate,
caloxydim (BAS 620H), carfentrazone-ethyl, chlomethoxyfen) chloramben,
chlorbromuron,
chloridazon, chlorimuron-ethyl, chlornitrofen, chlorotoluron, chlorpropham,
chlorsulfuron,
chlorthal-dimethyl, cinmethylin, cinosulfuron, clethodim, clomazone,
clopyralid,
clopyralid-olamine, cyanazine, cycloate, cyclosulfamuron, 2,4-D and its
butotyl, butyl,
isoctyl and isopropyl esters and its dimethylammonium, diolamine and trolamine
salts,
daimuron, dalapon, dalapon-sodium, dazomet, 2,4-DB and its dimethylammonium,
potassium and sodium salts, desmedipham, desmetryn, dicamba and its
diglycoiammonium,
dimethylammonium, potassium and sodium salts, dichlobenil, dichlorprop,
diclofop-methyl,
2-[4,5-dihydro-4-methyl-4-( 1-methylethyl)-5-oxo-1 H imidazol-2-yl)-5-methyl-3-
pyridinecarboxylic acid (AC 263,222), difenzoquat metilsulfate, diflufenican,
dimepiperate,
dimethenamid, dimethylarsinic acid and its sodium salt, dinitramine,
diphenamid, diquat
dibromide, dithiopyr, diuron, DNOC, endothal, EPTC, esprocarb, ethalfluraiin,
ethametsulfuron-methyl, ethofumesate, ethoxysulfuron, fenoxaprop-ethyl,
fenoxaprop-P-ethyl, fenuron, fenuron-TCA, flamprop-methyl, flamprop-M-
isopropyl,
flamprop-M-methyl, flazasulfuron, fluazifop-butyl, fluazifop-P-butyl,
fluchloralin,
flumetsulam, flumiclorac-pentyl, flumioxazin, fluometuron, fluoroglycofen-
ethyl, flupoxam,
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tlupyrsulfuron-methyl and its sodium salt, tluridone, tlurochloridone,
tluroxypyr)
tluthiacet-methyl, fomesafen, fosamine-ammonium, glufosinate, glufosinate-
ammonium,
glyphosate, glyphosate-isopropylammonium, glyphosate-sesquisodium,
glyphosate-trimesium, halosulfuron-methyl, haloxyfop-etotyl, haloxyfop-methyl,
hexazinone, imazamethabenz-methyl, imazamox, imazapyr, imazaquin,
imazaquin-ammonium, imazethapyr, imazethapyr-ammonium, imazosulfuron, ioxynil,
ioxynil octanoate, ioxynil-sodium, isoproturon, isouron, isoxaben,
isoxaflutole, lactofen,
lenacil, linuron, malefic hydrazide, MCPA and its dimethylammonium, potassium
and
sodium salts, MCPA-isoctyl, mecoprop, mecoprop-P, mefenacet, mefluidide,
metam-sodium, methabenzthiazuron, methylarsonic acid and its calcium,
monoammonium,
monosodium and disodium salts, methyl [[[ 1-[5-[2-chloro-4-
(trifluoromethyl)phenoxy]-2-
nitrophenyl]-2-methoxyethylidene]amino]oxy]acetate (AKH-7088), methyl S-
[[[[(4,6-
dimethyl-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-1-(2-pyridinyl)-1H
pyrazole-4-
carboxylate (NC-330), metobenzuron, metolachlor, metosulam, metoxuron,
metribuzin,
metsulfuron-methyl, molinate, monolinuron, napropamide, naptalam, neburon,
nicosulfuron,
norflurazon, oryzalin, oxadiazon, oxasulfuron, oxyfluorfen, paraquat
dichloride, pebulate,
pendimethalin, pentoxazone (KPP-314), perfluidone, phenmedipham, picloram,
picloram-potassium, pretilachlor, primisulfuron-methyl, prometon, prometryn,
propachlor,
propanil, propaquizafop, propazine, propham, propyzamide, prosulfuron,
pyrazolynate,
pyrazosulfuron-ethyl, pyridate, pyriminobac-methyl, pyrithiobac, pyrithiobac-
sodium,
quinclorac, quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-P-tefuryl,
rimsulfuron,
sethoxydim, siduron, simazine; sulcotrione (ICIAOOS 1 ), sulfentrazone,
sulfometuron-methyl,
TCA, TCA-sodium, tebuthiuron, terbacil, terbuthylazine, terbutryn,
thenylchlor,
thiafluamide (BAY 11390), thifensulfuron-methyl, thiobencarb, tralkoxydim, tri-
allate,
triasulfuron, triaziflam, tribenuron-methyl, triclopyr, triclopyr-butotyl,
triclopyr-triethylammonium, tridiphane, trifluralin, triflusulfuron-methyl,
and vernolate.
In certain instances, combinations with other herbicides having a similar
spectrum of
control but a different mode of action will be particularly advantageous for
preventing the
development of resistant weeds.
Preferred for better control of undesired vegetation in corn (e.g., lower use
rate,
broader spectrum of weeds controlled, or enhanced crop safety) or for
preventing the
development of resistant weeds in corn are mixtures of a compound of this
invention with
one or more of the herbicides selected from the group thifensulfuron-methyl,
rimsulfuron,
nicosulfuron, primisulfuron, atrazine, terbuthylazine, 2,4-D, dicamba,
bromoxynil)
imazethapyr, clopyralid, prosulfuron, glyphosate, glyphosate-trimesium,
glufosinate,
fluthiacet-methyl, quizalofop-P-ethyl, bentazone, flumetsulam, halosulfuron,
sethoxydim,
and flumiclorac-pentyl.
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Specifically preferred mixtures for use in corn are selected from the group:
a) Preparation of 2-[(2,3-dihydro-~,8-dimethylspiro[4H 1-benzothiopyran-4,2'-
[1,3]dioxolanJ-6-yl)carbonyl]-1,3-cyclohexanedione S,S-dioxide monosodium salt
(mixture
partner A, generally applied at a rate of 4 to 280 g/ha, preferably applied at
a rate of 8 to 70
g/ha) in combination with:
Preferred Preferred
Combination Ratio Ratio Use Use Rate
Mixture Partner Range Range Rate Range
Number B of A:B Range of B
of A:B of (g/ha)
B (g/ha)
I rimsuifuron I:5-300:11:1-70:1I-20 1-10
2 thifensulfuron-methyl1:2-300:tI:I-70:l1-10 1-5
3 nicosulftuon 1:10-300:11:1-70:1t-50 1-10
4 rimsulfuron I:5-300:1l:l-70:11-20 1-10
in combination
with I:10-300:lI:I-70:tI-50 i-10
nicosulfuron
rimsulfuron 1:5-300:I1:1-70:II-20 1-10
in combination
with 1:2-300:11: I-70:1-10 1-5
thifensulfuron-methyl I
6 prosulfuron 1:10-300:12:1-70:1I-50 1-10
7 prosulfuron 1:l0-300:12:1-70:1I-50 1-10
in combination
with 1:10-300:12:1-70:1I-50 1-10
primisulfuron
8 atrazine 1:500-3:11:25-1:1100-2000100-500
9 terbuthylazine 1:500-3:11:25-l:l100-2000I00-500
IO dicamba 1:125-30:11:5-7:1 10-500 10-100
ll 2,4-D 1:250-6:11:25-l:l50-100050-500
12 bromoxynil 1:250-6:1I:25-1:150-I00050-500
13 imazethapyr l:25-300:11:2-14:11-100 5-50
14 glyphosate 1:250-6:1l:25-l:l50-I00050-500
glufosinate I:250-6:1l:25-l:l50-100050-500
16 glyphosate-trimesium1:250-6:1l:25-1:150-100050-500
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b) 2-[(2,3-dihydro-5,8-dimethylspiro(4N 1-benzothiopyran-4.2'-(1,3]dioxolan]-6-
yl)carbonyl]-1,3-cyclohexanedione S>S-dioxide monopotassium salt (mixture
partner A,
generally applied at a rate of 4 to 280 g/ha, preferably applied at a rate of
8 to 70 g/ha) in
combination with:
Preferred Preferred
Combination Ratio Ratio Use RateUse Rate
Mixture Partner Range Range Range Range
Number B of A:B of of B
of A:B B (g/ha)(g/ha)
1 rimsulfuron 1:5-300:l1:1-70:1I-20 I-10
2 thifensulfuron-methyl1:2-300:11:1-70:l1-10 1-5
3 nicosulfuron I:10-300:11:1-70:1I-50 I-10
4 rimsulfuron 1:5-300:1I:l-70:11-20 I-10
in combination
with 1:10-300:1I:I-70:1I-50 I-10
nicosulfuron
5 rimsulfuron 1:5-300:l1:1-70:11-20 1-10
in combination
with 1:2-300:11:1-70:1I-10 1-5
thifensulfuron-methyl
6 prosulfuron 1:10-300:12:1-70:I1-50 1-10
7 prosulfuron 1:10-300:I2:1-70:11-SO 1-10
in combination
with 1:10-300:12:1-70:I1-50 I-10
primisulfuron
8 atrazine 1:500-3 I :25-1:1100-2000100-500
:1
9 terbuthylazine t:500-3:l1:25-I:1100-2000100-500
dicamba 1:125-30:11:5-7:110-S00 10-I00
11 2,4-D 1:250-6:11:25-1:150-I000 50-500
12 bromoxynii 1:250-6:1I:25-I:150-I000 50-500
13 imazethapyr 1:25-300:Il:2-14:I1-100 5-50
14 glyphosate 1:250-6:1I:25-l:l50-t000 50-500
glufosinate 1:250-6:11:25-1:150-l000 50-500
16 glyphosate-trimesium1:250-6:11:25-I:l50-1000 ~0-500
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c) (?.3-dihydro-~.8-dimethylspiro[4tl- I -benzothiopyran-4,?'-[ I ,3
]dioxolan]-6-yl)( 1-
ethyl-~-hydroxy-1H-pyrazol-4-yl)methanone S,S-dioxide monopotassium salt
(mixture
partner A, generally applied at a rate of 4 to 280 g/ha, preferably applied at
a rate of 8 to 70
5 g/ha) in combination with:
Preferred Preferred
Combination Ratio Ratio Use Use Rate
Mixture Partner Range Range Rate Range
Number B of A:B Range of B
of A:B of (g/ha)
B (g/ha)
1 rimsulfuron 1:5-300:11:1-70:11-20 1-10
2 thifensulfuron-methyl1:2-300:11:1-70:11-10 I-5
3 nicosuifuron 1:10-300:1I:1-70:1I-50 1-10
4 rimsulfuron 1:5-300:11:1-70:lI-20 1-10
in combination
with 1:10-300:II:l-70:11-50 I-10
nicosulfuron
5 rimsulfuron 1:5-300:11:1-70:II-20 1-10
in combination
with 1:2-300:11: I-70:1I-10 I-5
thifensulfuron-methyl
6 prosulfuron 1:10-300:12:1-70:1I-50 I-10
7 prosuifuron I:10-300:12:1-70:11-50 I-10
in combination
with 1:10-300:12:1-70:11-50 1-10
primisulfuron
8 atrazine 1:500-3:ll:25-1:1100-2000i00-500
9 terbuthylazine 1:500-3:11:25-1:1100-2000100-500
10 dicamba l:125-30:11:5-7:1 10-500 10-I00
11 2,4-D 1:250-6:11:25-1:150-100050-500
12 bromoxynil 1:250-6:11:25-1:150-I00050-500
13 imazethapyr 1:25-300:I1:2-14:11-100 5-50
14 glyphosate 1:250-6:11:2S-l:l50-100050-500
15 glufosinate 1:250-6:11:25-I:150-I00050-S00
16 glyphosate-trimesium1:2S0-6:11:2~-l:l50-l00050-500
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Gl
d) (2.3-dihydro-5,8-dimethylspiro[4H 1-benzothiopyran-4.2'-[ 1,3 ]dioxolan]-6-
yl)( 1-
ethyl-5-hydroxy-1 H pyrazol-4-yl)methanone S. S-dioxide monosodium salt
(mixture partner
A, generally applied at a rate of 4 to 280 g/ha, preferably applied at a rate
of 8 to 70 g/ha) in
combination with:
Preferred Preferred
Combination Ratio Ratio Use RateUse Rate
Mixture Partner Range Range Range Range
Number B of A:B of of B
of A:B B (g/ha)(g/ha)
1 rimsulfuron I:5-300:11:l-70:11-20 1-10
2 thifensulfuron-methyli:2-300:1I:l-70:1I-10 I-5
3 nicosulfuron 1:10-300:ll:l-70:1I-50 1-10
4 rimsulfuron 1:5-300:l1:1-70:11-20 1-10
in combination
with I:10-300:I1:1-70:1!-50 1-10
nicosulfuron
rimsulfuron I:5-300:11:1-70:11-20 1-10
in combination
with 1:2-300:1I :1-70:11-10 I -5
th ifensulfuron-methyl
6 prosulfuron 1:10-300:12:1-70:II-50 I-10
7 prosulfuron I:10-300:I2:1-70:11-50 1-10
in combination
with I:10-300:12:1-70:1I-50 1-10
primisuifuron
8 atrazine 1:500-3:11:25-1:1100-2000100-500
9 terbuthylazine l:500-3:11:25-1:1100-2000100-500
dicamba 1:125-30:I1:5-7:1!0-500 10-100
11 2,4-D 1:250-6:11:25-I:I50-1000 50-500
12 bromoxynil 1:250-6:11:25-1:150-1000 50-500
13 imazethapyr 1:25-300:11:2-14:11-100 5-50
14 glyphosate 1:250-6:11:25-I:150-1000 50-500
glufosinate 1:250-6:1I:25-l:l50-1000 50-500
16 giyphosate-trimesium1:250-6:11:25-l:l50-1000 50-500
A herbicidally effective amount of the compounds of this invention is
determined by a
number of factors. These factors include: formulation selected, method of
application,
amount and type of vegetation present, growing conditions, etc. In general, a
herbicidally
10 effective amount of compounds of this invention is 0.001 to 20 kg/ha with a
preferred range
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62
of 0.004 to 1.0 kg/ha. One skilled in the art can easily determine the
herbicidally effective
amount necessary for the desired level of weed control.
The following Tests demonstrate the control efficacy of the compounds of this
invention against specific weeds. The weed control afforded by the compounds
is not
limited, however, to these species. See Index Tables A-C for compound
descriptions. The
abbreviation "dec." indicates that the compound appreared to decompose on
melting. The
abbreviation "Ex." stands for "Example" and is followed by a number indicating
in which
example the compound is prepared. An "-" indicates that a melting point is not
available.
INDEX TABLE A
OM
~S O~ ~R6
~0~2 5
R
Cmpd R4 RS R6 M+ m C
1 Cl Cl H (HSCZ)3NH+ 140 (dec.)
2 CH3 CH3 CH3 (HSC2)3NH+ 115 (dec.)
3 (Ex. CH3 CH3 H Na+ >215
4)
4 (Ex. CH3 CH3 H K+ >215
3)
5 (Ex. CHI CH3 H Li+ 266-267
2) *
6 (Ex. CH3 CH3 H (Ct6H33)(CH3)2(C6H5CH2)N+-
5)
7 CH3 CH3 H (CH3)3(C6HsCH2)N+
8 CH3 CH3 H ((CH3)3CCH2(CH3)2C-4-C6H4-_
(OCH2CH2)2)(CH3)2-
(C6HSCH2)N+
9 CH3 CH3 H (HSC2)3NH+ l98-205
* See
Index
Table
C far
~ H
NMR
data.
INDEX
TABLE
B
Cmpd Structure mph
10 (Ex. ~ C H3 p O'K+ >260 *
1 )
O~ WN~C2H5
N
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11 ~~ ~y~3 p O Na+ >2S0
~~N~COHS
~N
(0),
12
CHI O O Na+
0
~~ N~ CH;
N
S
~O)2
13 280-285
14 130-140
~3
15 - Ja+ >2S0
N--C2H5
* See Index Table C for 1 H NMR data.
INDEX TABLE C
Cmpd No. 1H NMR Data ((CD3)2S0 solution unless indicated otherwise)a
3 8 1.67-1.8 (m, 2H)) 2.0-2.2 (m, 7H), 2.4-2.57 (m, SH), 3.4-3.5 (m) 2H),
4.05-4.25 (m, 4H)) 6.76 (s, 1 H).
4 8 1.65-l.78 (m, 2H), 2.0-2.15 (m, 7H), 2.4-2.53 (m) SH), 3.4-3.5 (m, 2H),
4.05-4.25 (m, 4H), 6.76 (s) I H).
8 1.75-l.85 (m, 2H), 2.08 (s, 3H), 2.2-2.35 (m) 4H), 2.4-2.6 (m, SH), 3.42-
3.54 (m, 2H), 4.05-4.25 (m, 4H)) 6.83 (s, i H).
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6~
~ 1.09 (br t. 3H)) 2.17 (s, 3H), 2.4-2.6~ (m. Sf-1), 3.3-3.7 (m, 4H), 4-4.3
(m,
4H), 6.5~ (br s. 1 H), 7. I (br s, I H).
I 1 cS I.13 (t, 3H), 2.19 {s, 3H), 2.4-2.5~ (m, 2H), ?.6 (s. 3H), 3.4-3.7 (m)
4H),
4-4.3 (m, 4H), 6.65 (br s, l H), 7. l4 (s, 1 H).
12 b 2.17 (s, 3H)) 2.4-2.~~ (m, 2H)) 2.59 (s, 3H), 3.17 (s, 3H), 3.49 (m) 2H),
4. l-4.3 (m, 4H)) 6.6 (br s, 1H), 7.1 (br s, 1H).
13 b I.15-1.24 (m, 6H), 1.65-1.75 (t, 2H), 2.10-2.20 (m) 3H), 2.25 (s, 3H),
3.3Q-3.4~ (m, 2H), 2.50-2.55 (m, 4H), 3.35-3.45 (m, 2H), 4.50-4.60 (m,
2H), 6.76 (s, 1 H).
14 (CDCl3) 8 1.I7-l.23 (t, 9H), 1.29-1.31 (d, 6H), 1.90-1.95 (t, 2H), 2.40 (s,
3H), 2.43-2.5 (t, 4H), 2.60-2.65 (t, 2H), 2.69 (s, 3H), 2.90-3.03 (q, 6H),
3.40-3.45 (t, 2H), 4.40-4.45 (m, 2H), 6.91 (s, 1H).
8 1.13 (t) 3H), 2.32 (s, 3H), 2.62 (s, 3H), 3.19 (m, 2H), 3.6 (m, 2H), 3.93
(m, 2H), 6.8 (br s, 1 H), 7.32 (s, 1 H).
a 1H NMR data are in ppm downfield from tetramethylsilane. Couplings are
designated by
(s)-singlet, (d)-doublet, (t)-triplet, (q)-quartet, (m)-multiplet, and (br)-
broad.
BIOLOGICAL EXAMPLES OF THE INVENTION
5 TEST A
Seeds of barley (Hordeum vulgare), barnyardgrass (Echinochloa crus-galli),
bedstraw
(Galium aparine), blackgrass (Alopecurus myosuroides), chickweed (Stellaria
media),
cocklebur (Xanthium strumarium), corn (Zea mays), cotton (Gossypium hirsutum),
crabgrass
(Digitaria sanguinalis), downy brume (Bromus tectorum), giant foxtail (Setaria
faberii),
10 lambsquarters (Chenopodium album), morningglory (Ipomoea hederacea), rape
(Brassica
napus}, rice (Oryza sativa), sorghum (Sorghum bicolor), soybean (Glycine max),
sugar beet
(Beta vulgaris), velvetleaf (Abutilon theophrasti), wheat (Triticum aestivum),
wild
buckwheat (Polygonum convolvulus), wild oat (Avena fatua) and purple nutsedge
(Cyperus
rotundus) tubers were planted and treated preemergence with test chemicals
formulated in a
I S non-phytotoxic solvent mixture which included a surfactant.
At the same time, these crop and weed species were also treated with
postemergence
applications of test chemicals formulated in the same manner. Plants ranged in
height from
2 to I 8 cm ( 1- to 4-leaf stage) for postemergence treatments. Treated plants
and controls
were maintained in a greenhouse for twelve to sixteen days, after which a11
species were
compared to controls and visually evaluated. Plant response ratings,
summarized in Table B,
are based on a scale of 0 to 10 where 0 is no effect and 10 is complete
control. A dash (-)
response means no test result.
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Table A COMPOUND Table A COMPOUND
Rate 400 g/ha 1 9 1314 Rate 400 g/ha 1 9 13
14
POSTEMERGENCE PREEMERGENCE
B. signalgrass- - 9 9 B. signalgrass - - 9
9
Barley 5 9 - - Barley 0 0 -
-
Barnyardgrass 9 9 - - Barnyardgrass 5 9 -
-
Bedstraw 9 10 9 9 Bedstraw 5 8 8
9
Blackgrass 7 9 8 8 Blackgrass 2 1 3
2
Chickweed 8 l0 - - Chickweed 4 9 -
-
Cocklebur 9 9 9 ZO Cocklebur 6 8 8
7
Corn 2 2 2 4 Corn 0 0 0
0
Cotton 1010 - - Cotton 8 10 -
-
Crabgrass 7 9 9 10 Crabgrass 8 10 10
10
Downy brome 6 9 - - Downy brome 6 8 -
-
Giant foxtail 5 9 8 9 Giant foxtail 2 3 6
2
Lambsquarters 9 9 - - Lambsquarters 109 -
-
Morningglory 1010 9 10 Morningglory 6 8 9
8
Nutsedge 2 8 9 8 Nutsedge 3 8 8
10
Rape 109 7 9 Rape 9 2 7
9
Redroot pigweed- - 9 9 Redroot pigweed - - l0
10
Rice 9 10 - - Rice 7 9 -
-
Sorghum 9 10 - - Sorghum 2 2 -
-
Soybean 9 10 1010 Soybean 6 9 9
9
Sugar beet 1010 1010 Sugar beet 1010 10
10
Velvetleaf 10l0 9 10 Velvetleaf l010 l0
10
Wheat 8 9 9 8 Wheat 0 5 1
3
Wild buckwheat6 8 - - Wild buckwheat 6 3 -
-
Wild oat 4 8 2 5 Wild oat 0 6 3
1
Table A COMPOUND Table A COMPOUND
Rate 20D g/ha 2 3 4 5 Rate 200 g/ha 2 3 4
5
POSTEMERGENCE PREEMERGENCE
B, signalgrass- - - - B. signalgrass - - -
-
Barley 6 8 9 9 Barley 0 0 0
0
Barnyardgrass 9 9 9 10 Barnyardgrass 9 9 9
9
Bedstraw 9 9 9 10 Bedstraw 8 7 8
8
Blackgrass 6 6 7 9 Blackgrass 0 2 1
0
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Chickweed 9 9 9 10 Chickweed 6 7 9
9
Cocklebur 1010 1010 Cocklebur 4 4 6
9
Corn 2 3 2 2 Corn 0 0 0
1
Cotton 1010 1010 Cotton 0 3 3
2
Crabgrass 9 10 9 10 Crabgrass 1010 10
10
Downy brome 5 7 7 9 Downy brome 0 0 0
5
Giant foxtail 7 9 9 9 Giant foxtail 0 1 2
3
Lambsquarters 9 9 9 10 Lambsquarters 9 10 10
10
Morningglory 9 10 ZO10 Morningglory 2 3 3
9
Nutsedge - - - 9 Nutsedge - - -
2
Rape 108 6 9 Rape 0 0 0
0
Redroot pigweed- - - - Redroot pigweed - - -
-
Rice 9 9 9 10 Rice 8 7 6
8
Sorghum 8 9 9 9 Sorghum 0 0 0
2
Soybean 1010 1010 Soybean 4 8 6
7
Sugar beet 1010 1010 Sugar beet 9 l0 l0
10
Velvetleaf 1010 1010 Velvetleaf 1010 10
10
Wheat 8 9 9 9 Wheat 1 0 0
1
Wild buckwheat7 6 4 2 Wild buckwheat 0 2 4
0
Wild oat 5 7 8 8 Wild oat 1 0 1
3
Table A COMPOUND Table A COMPOUND
Rate 100 g/ha 1 9 1314 Rate 100 g/ha 1 9 13
14
POSTEMERGENCE PREEMERGENCE
B. signalgrass- - B 7 B. signalgrass - - 8
4
Barley 4 8 - - Barley 0 0 -
-
Barnyardgrass B 9 - - Barnyardgrass 1 8 -
-
Bedstraw 9 9 9 9 Bedstraw 6 2 8
9
Blackgrass 5 5 6 4 Blackgrass 1 0 0
0
Chickweed 7 9 - - Chickweed 3 5 -
-
Cocklebur 9 9 9 10 Cocklebur 2 0 8
1
Corn 1 0 1 0 Corn 0 0 0
0
Cotton 1010 - - Cotton 3 0 -
-
Crabgrass 2 9 9 8 Crabgrass 7 8 9
7
Downy brome 5 8 - - Downy brome 0 0 -
-
Giant foxtail 3 8 6 7 Giant foxtail 1 1 1
0
Lambsquarters 9 9 - - Lambsquarters 9 9 -
-
Morningglory l010 9 10 Morningglory 5 1 8
4
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Nutsedge 2 8 8 6 Nutsedge - 0 1 0
Rape 8 6 S 7 Rape 3 0 0 0
Redroot pigweed - - 9 9 Redroot pigweed - - l0 9
Rice 9 10- - Rice 7 8 - -
Sorghum 9 8 - - Sorghum 1 2 - -
Soybean 8 1010 10 Soybean 5 8 9 8
Sugar beet 10 1010 10 Sugar beet 10 1010 10
Velvetleaf 10 109 10 Velvetleaf 9 1010 10
Wheat 6 9 8 6 Wheat 0 0 0 0
Wild buckwheat 6 6 - - Wild buckwheat 2 0 - -
Wild oat 3 3 1 2 Wild oat 0 1 2 0
Table A COMPOUND Table A COMPOUND
Rate 50 g/ha 2 3 4 5 10 Rate 50 g/ha 2 3 4 5
10
POSTEMERGENCE PREEMERGENCE
B. signalgrass - - - - - B, signalgrass - - - -
-
Barley 5 7 8 8 1 Barley 0 0 0 0
0
Barnyardgrass 9 9 9 9 9 Barnyardgrass 8 7 0 7
5
Bedstraw 7 9 9 9 9 Bedstraw 6 7 7 8
2
Blackgrass 4 5 4 6 3 Blackgrass 0 0 0 0
0
Chickweed 7 9 9 9 10 Chickweed 1 4 5 7
0
Cocklebur 9 1010 109 Cocklebur 0 2 1 1
0
Corn 1 1 2 1 1 Corn 0 0 0 0
0
Cotton 10 1010 109 Cotton 0 2 2 0
0
Crabgrass 5 9 9 109 Crabgrass 1 109 9
6
Downy brome 3 3 5 5 0 Downy brome 0 0 0 1
0
Giant foxtail 3 6 6 8 9 Giant foxtail 0 0 1 0
2
Lambsquarters 9 9 9 109 Lambsquarters 9 1010 9
10
Morningglory 9 1010 108 Morningglory 0 0 1 3
0
Nutsedge 8 - - 6 0 Nutsedge - - - 0
0
Rape 6 3 4 6 7 Rape 0 0 0 0
0
Redroot pigweed - - - - - Redroot pigweed - - - -
-
Rice 9 9 9 109 Rice 6 3 3 7
0
Sorghum 4 7 6 6 8 Sorghum 0 0 0 0
0
Soybean 10 1010 108 Soybean 3 5 6 6
0
Sugar beet 9 9 9 1010 Sugar beet 4 9 9 10
4
Velvetleaf 10 1010 1010 Velvetleaf 8 8 9 10
6
Wheat 7 7 8 7 3 Wheat 0 0 0 0
0
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Wild buckwheat7 3 3 0 7 Wild buckwheat 0 0 0 0 0
Wild oat 3 4 7 2 5 Wild oat 0 0 0 0 0
Table A COMPOUND Table A COMPOUND
Rate 400 13 14 Rate 100 g/ha 13 14
g/ha
SPRAYED PADDY SPRAYED PADDY
Barnyardgrass9 10 Barnyardgrass 9 10
Ducksalad 8 9 Ducksalad 8 7
Rice 9 9 Rice 8 9
S. flatsedge9 8 S. flatsedge 8 6
TEST B
The compounds evaluated in this test were formulated in a non-phytotoxic
solvent
mixture which included a surfactant and applied to the soil surface before
plant seedlings
emerged (preemergence application), to water that covered the soil surface
(flood
application), and to plants that were in the 1- to 4-leaf stage (postemergence
application). A
sandy loam soil was used for the preemergence and postemergence tests, while a
silt loam
soil was used in the flood test. Water depth was approximately 2.5 cm for the
flood test and
was maintained at this level for the duration of the test.
Plant species in the preemergence and postemergence tests consisted of
barnyardgrass
(Echinochloa crus-galli), barley (Hordeum vulgare), bedstraw (Galium aparine),
blackgrass
(Alopecurus myosuroides), chickweed (Stellaria media), cocklebur (Xanthium
strumarium),
corn (Zea mays cv. Pioneer 3394), cotton (Gossypium hirsutum), crabgrass
(Digitaria
sanguinalis), downy brome (Bromus tectorum), giant foxtail (Setaria faberii),
johnsongrass
(Sorghum halpense), lambsquarters (Chenopodium album), morningglory (Ipomoea
hederacea), pigweed (Amaranthus retroflexus), rape (Brassica napus), ryegrass
(Lolium
multiflorum), soybean (Glycine max), speedwell ( heronica persica), sugar beet
(Beta
vulgaris), velvetleaf (Abutilon theophrasti), wheat (Triticum aestivum), wild
buckwheat
{Polygonum convolvulus), and wild oat (Avena fatua).
Plant species in the flood test consisted of rice (Oryza saliva), umbrella
sedge (Cyperus
difformis), duck salad (Heteranthera limosa), barnyardgrass (Echinochloa crus-
galli,
designated as 'barnyardgrassl') and late watergrass (Echinochloa oryzicola)
grown to the 2-
leaf stage for testing.
A11 plant species were planted one day before application of the formulated
compound
for the preemergence portion of this test. Plantings of these species were
adjusted to produce
plants of appropriate size for the postemergence portion of the test. All
plant species were
grown using normal greenhouse practices. Visual evaluations of injury
expressed on treated
plants, when compared to untreated controls, were recorded approximately
fourteen to
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69
twenty-one days after application of the test compound. Plant response
ratings, summarized
in Table B, were recorded on a 0 to 100 scale where 0 is no effect and 100 is
complete
control. A dash (-) response means no test result.
Table B COMPOUND Table B COMPOUND Table B COMPOUND
Rate 250 g/ha 1 Rate 250 g/ha 1 Rate 125 g/ha 1 13
POSTEMERGENCE PREEMERGENCE POSTEMERGENCE
Barley (winter) 15 Barley (winter) 0 Barley (winter)0 -
Barnyardgrass 80 Barnyardgrass 95 Barnyardgrass 70 -
Barnyardgrass 1 70 Bedstraw 80 Barnyardgrass 60 40
1
Bedstraw 90 Blackgrass 0 Bedstraw 90 -
Blackgrass 40 Chickweed 0 Blackgrass 30 -
Chickweed 65 Cocklebur 50 Chickweed 65 -
Cocklebur 90 Corn 1 0 Cocklebur 90 -
Corn 1 0 Cotton 70 Corn 1 0 -
Cotton 90 Crabgrass 100 Cotton 90 -
Crabgrass 85 Downy brome 0 Crabgrass 75 -
Downy brome 25 Giant foxtail 85 Downy brome 20 -
Ducksalad 45 Italn. ryegrass 0 Ducksalad 30 65
Giant foxtail 50 Johnsongrass 30 Giant foxtail 40
Italn. ryegrass 0 Lambsquarter 90 Italn. ryegrass0 -
Johnsongrass - Morningglory 100 Johnsongrass - -
Lambsquarter 95 Rape 95 Lambsquarter 95 -
Late watergrass 75 Redroot pigweed - Late watergrass65
Morningglory 90 Soybean 90 Morningglory 90 -
Rape 95 Speedwell 100 Rape 95 -
Redroot pigweed 90 Sugar beet 10o Redroot pigweed90 -
Rice japonica 60 Velvetleaf l00 Rice japonica 40 0
Soybean 90 Wheat 0 Soybean 80 -
Speedwell 100 Wild buckwheat to Speedwell 95 -
Sugar beet 100 Wild oat 0 Sugar beet 100 -
Umbrella sedge 50 Umbrella sedge 40 75
Velvetleaf 100 Velvetleaf 100 -
Wheat 25 Wheat 0 -
Wild buckwheat 65 Wild buckwheat 65 -
Wild oat 0 wild oat 0
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Table B COMPOUND Table B COMPOUND
Rate 125 g/ha 1 Rate 62 g/ha 1 2 3 4 5 10 13
PREEMERGENCE POSTEMERGENCE
Barley (winter)0 Barley (winter) 10 30 20 30 30 10 -
Barnyardgrass 50 Barnyardgrass 50 95 90 90 90 90 -
Bedstraw 65 Barnyardgrass 1 0 15 35 60 75 10 30
Blackgrass 0 Bedstraw 55 80 80 80 90 80 -
Chickweed 0 Blackgrass 30 30 30 40 35 20 -
Cocklebur 40 Chickweed SO 90 90 - 10095 -
Corn 1 0 Cocklebur 90 90 90 90 90 90 -
Cotton 40 Corn 1 30 0 35 0 0 0 -
Crabgrass 90 Cotton 10095 90 90 10040 -
Downy brome - Crabgrass 75 80 90 90 90 95 -
Giant foxtail 40 Downy brome 25 10 30 30 35 10 -
Italn. ryegrass0 Ducksalad 0 80 70 70 90 60 50
Johnsongrass 20 Giant foxtail 30 70 60 70 80 100 -
Lambsquarter 90 Italn. ryegrass 0 0 20 30 20 20 -
Morningglory 75 Johnsongrass 55 30 50 70 70 90 -
Rape 30 Lambsquarter 100100 90 80 90 100 -
Redroot pigweed- Late watergrass 0 - - - - - -
Soybean 70 Morningglory 90 85 90 90 90 90
Speedwell 90 Rape 90 40 20 20 50 20 -
Sugar beet 100 Redroot pigweed 80 80 80 85 100100
Velvetleaf 100 Rice japonica 10 0 30 30 50 0 0
Wheat 0 Soybean 90 90 90 90 90 70 -
Wild buckwheat0 Speedwell 95 70 90 90 80 95 -
Wild oat 0 Sugar beet 10070 - 90 100100 -
Umbrella sedge 0 70 70 60 70 40 55
Velvetleaf 95 100 90 90 l0095 -
Wheat 30 10 40 40 50 0 -
Wild buckwheat 35 30 20 30 20 70 -
Wild oat 0 30 30 30 25 30 -
5
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Table B COMPOUND
Rate 62 g/ha 1 2 3 4 5 10
PREEMERGENCE
Barley (winter) 0 0 0 0 0 0
Barnyardgrass 0 40 20 35 50 0
Bedstraw 10 20 80 40 90 70
Blackgrass 0 10 0 0 0 0
Chickweed 0 65 70 80 65 60
Cocklebur 20 - 50 35 50 100
Corn 1 0 0 20 0 0 0
Cotton 30 0 10 40 40 0
Crabgrass 40 90 80 85 85 100
Downy brome 0 0 0 20 0 0
Giant foxtail 20 10 35 30 15 30
Italn. ryegrass 0 0 0 0 0 0
Johnsongrass 0 0 0 20 0 0
Lambsquarter 95 90 90 90 95 100
Morningglory 50 50 30 40 60 0
Rape 0 10 0 0 0 0
Redroot pigweed 75 40 30 60 30 30
Soybean 40 10 10 40 50 0
Speedwell 95 40 80 60 50 -
Sugar beet 100 50 70 90 100 40
Velvetleaf 90 90 100 100 100 100
Wheat 0 10 0 0 0 0
Wild buckwheat 0 10 0 30 0 0
Wild oat 0 10 0 0 0 0
Table B COMPOUND
Rate 31 g/ha 1 2 3 4 5 10 13
POSTEMERGENCE
Barley (winter) 10 10 10 20 15 0 -
Barnyardgrass 40 90 90 90 90 90 -
Barnyardgrass 1 0 10 30 35 50 10 20
Bedstraw 45 70 70 80 80 70 -
Blackgrass 30 20 20 30 25 10 -
Chickweed 10 90 90 90 100 90 -
Cocklebur 90 90 90 90 90 90 -
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Corn 1 0 0 10 0 0 0 -
Cotton 90 90 90 90 90 30 -
Crabgrass 60 70 85 90 90 90 -
Downy brome 0 0 10 0 25 0 -
Ducksalad 0 70 50 50 80 20 0
Giant foxtail 20 30 50 60 60 95
Italn. ryegrass 0 0 10 10 10 10 -
Johnsongrass 45 20 40 50 40 40 -
Lambsquarter 95 95 90 80 90 100 -
Late watergrass o - - - - - -
Morningglory 90 ?0 90 90 90 - -
Rape 90 0 0 0 40 0 -
Redroot pigweed 80 50 80 80 90 95 -
Rice japonica 10 0 30 20 20 0 0
Soybean 90 90 80 90 90 50 -
Speedwell 70 70 80 80 80 90 -
Sugar beet 100 70 90 90 l00 100 -
Umbrella sedge 0 60 60 60 50 30 20
Velvetleaf 95 90 90 90 100 95 -
Wheat 25 0 30 30 35 0 -
Wild buckwheat 30 20 20 20 10 70 -
Wild oat 0 20 10 10 0 20 -
Table B COMPOUND
Rate 31 g/ha 1 2 3 4 5 10
PREEMERGENCE
Barley (winter) 0 0 0 0 0 0
Barnyardgrass 0 0 l0 0 30 0
Bedstraw 10 10 30 40 0 20
Blackgrass 0 0 0 0 0 0
Chickweed 0 l0 70 70 0 50
Cocklebur l0 0 l0 l0 20 70
Corn 1 0 0 0 0 0 0
Cotton 10 0 0 20 20 0
Crabgrass 20 70 60 50 70 100
Downy brome 0 0 0 0 0 0
Giant foxtail 0 0 10 0 0 20
Italn. ryegrass 0 0 0 0 0 0
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Johnsongrass 0 0 0 0 0 0
Lambsquarter 95 90 90 90 80 95
Morningglory 10 50 0 20 0 0
Rape 0 0 0 0 0 0
Redroot pigweed 20 0 20 30 - 30
Soybean 10 0 0 20 30 0
Speedwell 95 20 80 0 50 -
Sugar beet 100 20 60 70 100 0
Velvetleaf 0 90 70 95 100 50
Wheat 0 0 0 0 0 0
Wild buckwheat o 0 0 0 0 0
Wild oat 0 0 0 0 0 0
Table B COMPOUND
Rate 16 g/ha 1 2 3 4 5 10 13
POSTEMERGENCE
Barley (winter) 10 0 0 0 10 0 -
Barnyardgrass 20 90 90 90 90 90 -
Barnyardgrass 1 0 0 20 20 20 0 15
Bedstraw 40 40 60 70 70 ?0 -
Blackgrass 10 0 10 30 0 0 -
Chickweed 10 80 90 80 90 90 -
Cocklebur 90 90 90 90 90 80 -
Corn 1 0 0 0 0 0 0
Cotton 90 80 80 80 90 - -
Crabgrass 40 40 80 BO 90 90 -
Downy brome 0 0 0 0 l0 0 -
Ducksalad 0 40 20 0 70 0 0
Giant foxtail 10 20 40 40 60 70 -
Italn. ryegrass 0 0 0 0 0 0 -
Johnsongrass 35 0 30 40 20 30 -
Lambsquarter 90 80 80 70 90 95
Late watergrass 0 - - - - - -
Morningglory 90 70 90 90 90 90 -
Rape 7 0 0 0 0 0 0 -
Redroot pigweed 60 40 80 70 80 90 -
Rice japonica 0 0 l0 0 0 0 0
Soybean 80 90 80 90 90 50 -
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Speedwell 40 - 60 e0 60 80 -
Sugar beet 100 60 90 90 100 100 -
Umbrella sedge 0 40 40 20 35 0 0
Velvetleaf 90 90 90 90 100 95 -
Wheat 0 0 20 20 20 0
Wild buckwheat 20 10 10 10 10 30 -
Wild oat 0 0 0 0 0 l0 -
Table B COMPOUND
Rate 16 g/ha 1 2 3 4 5 10
PREEMERGENCE
Barley (winter) 0 0 0 0 0 0
Barnyardgrass 0 0 0 0 10 0
Bedstraw 0 0 0 30 0 20
Blackgrass 0 0 0 0 0 0
Chickweed 0 0 60 30 0 0
Cocklebur 0 0 0 0 10 0
Corn 1 0 0 0 0 0 0
Cotton 0 0 0 10 0 0
Crabgrass 0 10 0 30 40 95
Downy brome 0 0 0 0 0 0
Giant foxtail 0 0 0 0 0 0
Italn. ryegrass 0 0 0 0 0 0
Johnsongrass 0 0 0 0 0 0
Lambsquarter 95 90 80 90 70 95
Morningglory 0 10 0 0 0 0
Rape 0 0 0 0 0 0
Redroot pigweed 0 0 0 20 0 10
Soybean 10 0 0 0 l0 0
Speedwell 0 0 70 0 - -
Sugar beet 100 0 0 60 40 0
Velvetleaf 0 80 40 10 70 0
Wheat 0 0 0 0 0 0
Wild buckwheat 0 0 0 0 0 0
Wild oat 0 0 0 0 0 0
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TEST C
Compounds evaluated in this test were formulated in a non-phytotoxic solvent
mixture
which inciuded a surfactant and applied to plants that were grown for various
periods of time
before treatment (postemergence application). A mixture of sandy loam soil and
greenhouse
~ potting mix in a 60:40 ratio was used for the postemergence test.
Plantings of these crops and weed species were adjusted to produce plants of
appropriate size for the postemergence test. All plant species were grown
using normal
greenhouse practices. Crop and weed species include American black nightshade
(Solanum
americanum), arrowleaf sida (Silo rhombifolia), barnyardgrass (Echinochloa
crus-galli),
cocklebur (Xanthium strumarium), common ragweed (Ambrosia elatior), common
lambsquarters (Chenopodium album), corn (Zea mays), cotton (Gossypium
hirsutum), eastern
black nightshade (Solanum ptycanthum), fall panicum (Panicum dichotomi,
florum), field
bindweed (Convolvulus arvensis), Florida beggarweed (Desmodium purpureum),
giant
foxtail {Setaria faberii), hairy beggarticks (Bidens pilosa), ivyleaf
morningglory (Ipomoea
hederacea), johnsongrass (Sorghum halepense), ladysthumb (Polygonum
persicaria), large
crabgrass (Digitaria sanguinalis), purple nutsedge (Cyperus rotundas), redroot
pigweed
(Amaranthus retroflexus), soybean (Glycine max), surinam grass (Brachiaria
decumbens),
velvetleaf (Abutilon theophrasti) and wild poinsettia (Euphorbia
heterophylla).
Treated plants and untreated controls were maintained in a greenhouse for
approximately 14 to 21 days, after which all treated plants were compared to
untreated
controls and visually evaluated. Plant response ratings, summarized in Table
C, were based
upon a 0 to 100 scale where 0 was no effect and 100 was complete control. A
dash response
(-) means no test result.
Table C COMPOUND
Rate 35 g/ha 3 4 5 9 10 11 14 15
POSTEMERGENCE
A. blacknightsh - - - - 100 - - -
Arrowleaf sida 50 20 80 90 10 60 60 20
Barnyardgrass 95 95 95 65 90 100 85 95
Cocklebur 95 95 95 100 95 100 85 85
Common ragweed 100 90 100 85 90 100 80 65
Corn 1 0 0 0 0 0 0 0 0
Cotton 95 95 100 90 BO 95 l00 60
E. blacknightsh 100 100 100 100 - 100 100 100
Fall panicum 80 BO 60 25 95 100 80 70
Field bindweed 85 90 80 60 70 60 80 20
F1. beggarweed Z00 80 - - - - -
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Giant foxtail 60 60 20 20 60 90 20 75
H. beggarticks 20 60 10 0 90 100 25 70
I. morningglory 100 85 100 80 80 85 95 50
Johnsongrass 5 5 0 0 0 60 10 15
Ladysthumb 100 100 100 100 100 100 1o0 100
Lambsquarters 90 95 100 70 95 100 100 95
Large crabgrass 80 80 80 60 80 80 75 25
Purple nutsedge 80 30 20 0 0 5 0 0
Redroot pigweed 90 95 90 65 90 90 70 85
Soybean 1 95 95 100 100 80 90 95 40
Surinam grass 60 60 60 25 40 60 25 20
Velvetleaf 100 100 100 100 95 100 100 90
Wild poinsettia 100 90 100 65 5 60 95 80
TEST D
Compounds evaluated in this test were formulated in a non-phytotoxic solvent
mixture
which included a surfactant and applied to plants that were grown for various
periods of time
before treatment (postemergence application). A mixture of sandy loam soil and
greenhouse
potting mix in a b0:40 ratio was used for the postemergence test. Test
compounds were
applied 13 days after the last postemergence planting.
Plantings of these crops and weed species were adjusted to produce plants of
appropriate size for the postemergence test. All plant species were grown
using normal
greenhouse practices. Crop and weed species include bristly starbur
(Acanthospermun
hispidum), alexandergrass (Brachiaria plantaginea), American black nightshade
(Solanum
americanum), apple-of Peru (Nicandra physaloides), arrowleaf sida (Silo
rhombifolia),
broadleaf signalgrass (Brachiaria platyphylla), Brazilian sicklepod (Cassia
tora Brazilian},
capim-colchao (Digitaria horizontalis), soybean (Glycine max cv. Cristalina,
designated
'Soybean 1'), Florida beggarweed (Desmodium purpureum), hairy beggarticks
(Bidens
pilosa), slender amaranth (Amaranthus viridis), southern sandbar {Cenchrus
echinatus), tall
morningglory (Ipomoea purpurea), tropical spiderwort (Commelina benghalensis),
soybean
{Glycine max cv. W20, designated 'Soybean 2') and soybean {Glycine max cv. W4-
4,
designated 'Soybean 3'), corn (Zea mays) and wild pointsettia {Eupohorbia
heterophylla).
Treated plants and untreated controls were maintained in a greenhouse for
approximately 13 days, after which a11 treated plants were compared to
untreated controls
and visually evaluated. Plant response ratings, summarized in Table D, are
based upon a 0 to
l00 scale where 0 is no effect and 100 is complete control.
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Table D COMPOUND Table D COMPOUND
Rate 70 g/ha 4 11 15 Rate 35 g/ha 4 11
15
POSTEMERGENCE POSTEMERGENCE
Alexandergrass 90 100 95 Alexandergrass 80 80
60
Apple-of-Peru 100100 100 Apple-of-Peru 100 100
100
Arrowleaf sida 95 90 65 Arrowleaf sida 85 80
60
B. Signalgrass 75 70 80 B. Signalgrass 70 60
60
Blk nightshade 100100 100 Blk nightshade 100 100
100
Braz sicklepod 60 10 50 Braz sicklepod 55 10
40
Bristly starbur 85 100 70 Bristly starbur 100 100
25
Capim-Colch 80 80 80 Capim-Colch 75 60
20
Corn 10 10 15 Corn 10 5 5
F1. beggarweed 100- - F1. beggarweed 100 - -
H, beggarticks 70 90 100 H. beggarticks 60 80
80
Morningglory l0080 80 Morningglory 100 80
80
5. amaranth 70 100 100 S. amaranth 40 100
100
S. sandbar 65 BO 95 S. sandbar 55 80
85
Soybean 1 10095 90 Soybean 1 80 80
75
Soybean 2 l0095 80 Soybean 2 100 90
65
Soybean 3 10095 85 Soybean 3 l00 90
85
Tr. Spiderwort 75 l00 90 Tr. Spiderwort 70 90
75
Wild poinsettia 100100 100 Wild poinsettia 100 60
95
Table D COMPOUND Table D COMPOUND
Rate 17 g/ha 4 11 15 Rate 8 g/ha 15
POSTEMERGENCE POSTEMERGENCE
Alexandergrass 85 70 10 Alexandergrass l0
Apple-of-Peru l00100 95 Apple-of-Peru 80
Arrowleaf sida 85 50 20 Arrowleaf sida 20
B. Signalgrass 60 50 20 B. Signalgrass 10
Blk nightshade 100l00 100 Blk nightshade 100
Braz sicklepod 50 5 20 Braz sicklepod 10
Bristly starbur 10070 20 Bristly starbur 10
Capim-Colch 55 60 10 Capim-Colch 10
Corn 0 0 5 Corn 0
F1. beggarweed 100- - F1. beggarweed -
H. beggarticks 55 80 50 H. beggarticks 20
Morningglory B5 80 70 Morningglory 50
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S. amaranth 70 100 80 S. amaranth 60
S. sandbur 30 80 60 S. sandbur 10
Soybean 1 10080 65 Soybean 1 35
Soybean 2 80 70 50 Soybean 2 30
Soybean 3 75 85 40 Soybean 3 25
Tr. Spiderwort60 80 60 Tr. Spiderwort 40
Wild poinsettia75 0 80 Wild poinsettia 60
TEST E
Compounds evaluated in this test were formulated in a non-phytotoxic solvent
mixture
which included a surfactant and applied to plants that were in the 1- to 4-
leaf stage
(postemergence application). A mixture of sandy loam soil and greenhouse
potting mix in a
60:40 ratio was used for the postemergence test.
Plantings of these crops and weed species were adjusted to produce plants of
appropriate size for the postemergence test. All plant species were grown
using normal
greenhouse practices. Crop and weed species include annual bluegrass {Poa
annua),
blackgrass 2 (Alopecurus myosuroides), black nightshade (Solanum nigra),
chickweed
(Stellaria media), common poppy (Papaver rhoeas), deadnettle (Lamium
amplexicaule),
downy brome (Bromus tectorum), field violet (Viola arvensis), galium 2 (Galium
aparine),
green foxtail (Setaria viridis), jointed goatgrass (Aegilops cylindrica),
kochia (Kochia
scoparia), lambsquarters {Chenopodium album), littleseed canarygrass (Phalaris
minor),
rape 1 (Brassica napus cv. Westar), rape 2 (Brassica napus cv. Jet Neuf),
redroot pigweed
(Amaranthus retroflexus), Russian thistle (Salsola kali), Italian ryegrass
(Lolium
multiflorum), scentless chamomile (Matricaria inodora), spring barley (Hordeum
vulgare),
sugar beet (Beta vulgaris), sunflower (Helianthus annuus), ivyleaf speedwell
(Veronica
hederaefolia), winter wheat (Triticum aestivum cv. cymmit, designated
'wheat'), spring
wheat (Triticum aestivum), winter wheat (Triticum aestivum designated 'wheat
(winter)'),
wild buckwheat (Polygonum convolvulus), wild mustard (Sinapis arvensis), wild
oat (Avena
fatua) 1 to 2 leaf designated 'Wild oat 1' and 2 to 3 leaf designated 'Wild
oat 2', windgrass
(Apera spica-venti) and winter barley (Hordeum vulgare).
Treated plants and untreated controls were maintained in a greenhouse for
approximately 21 to 28 days, after which all treated plants were compared to
untreated
controls and visually evaluated. Plant response ratings, summarized in Table
E, are based
upon a 0 to 100 scale where 0 is no effect and 100 is complete control. A dash
response (-)
means no test result.
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Table E COMPOUND Table E COMPOUND
Rate 62 g/ha 2 4 5 Rate 31 g/ha 1 2 4 5
POSTEMERGENCE POSTEMERGENCE
Annual bluegras- - - Annual bluegras o 20 - -
Barley (winter)50 - - Barley (winter) 5 20 - -
Blackgrass 45 - - Blackgrass 2 0 50 - -
2
Blk nightshade- - - Blk nightshade 10o 95 - -
Chickweed - - - Chickweed o 70 - -
Common poppy - - - Common poppy - 20 - -
Deadnettle - - - Deadnettle 90 70 - -
Downy brome - - - Downy brome 10 10 - -
Field violet - - - Field violet 0 10d -
-
Galium 2 - - - Galium 2 65 60 - -
Green foxtail95 - - Green foxtail 10 80 - -
I. Ryegrass 20 - - I. Ryegrass 5 5 - -
Jointed goatgra- - - Jointed goatgra 5 5 - -
Kochia - - - Kochia 35 70 - -
Lambsquarters- - - Lambsquarters 100 90 - -
LS canarygrass- - - LS canarygrass o l0 - -
Rape 1 50 85 60 Rape 1 30 0 72 40
Rape 2 90 92 60 Rape 2 - 25 70
50
Redroot pigweed- - - Redroot pigweed 85 20 - -
Russian thistle- - - Russian thistle - 30 - -
Scentless - - - Scentless chamo 80 65 - -
chamo
Speedwell - - - Speedwell 30 - - -
Spring Barley65 - - Spring Barley l0 20 - -
Sugar beet - - - Sugar beet loo 100 -
-
Sunflower - - - Sunflower 75 50 - -
Veronica hedera- - - Veronica hedera - 85 - -
Wheat 35 - - Wheat - 15 - -
Wheat (spring)30 - - Wheat (spring) 15 25 - -
Wheat (winter)55 - - Wheat (winter) 15 35 - -
Wild buckwheat- - - Wild buckwheat 0 30 - -
Wild mustard 100 95 100 Wild mustard 100 100 90
100
Wild oat 1 - - - Wild oat 1 - 0 - -
Wild oat 2 60 - - Wild oat 2 5 60 - -
Windgrass - - - windgrass 0 20 - -
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Table E COMPOUND Table E COMPOUND
Rate 16 g/ha 1 2 4 5 Rate 8 g/ha 1 2 4 5
POSTEMERGENCE POSTEMERGENCE
Annual bluegraso - - - Annual bluegras 0 2 - -
Barley (winter)0 15 - - Barley (winter) 0 5 - -
Hlackgrass 0 35 - - Blackgrass 2 0 5 - -
2
Blk nightshade30 - - - Blk nightshade 10 75 - -
Chickweed 0 - - - Chickweed 0 60 - -
Common poppy - - - - Common poppy - 30 - -
Deadnettle 35 - - - Deadnettle 0 50 - -
Downy brome 0 - - - Downy brome 0 0 - -
Field violet 0 - - - Field violet 0 80 - -
Galium 2 10 - - - Galium 2 0 30 - -
Green foxtail5 65 - - Green foxtail 0 20 - -
I. Ryegrass 5 0 - - I. Ryegrass 0 0 - -
Jointed goatgra0 - - - Jointed goatgra 0 2 - -
Kochia 0 - - - Kochia 0 60 - -
Lambsquarters30 - - - Lambsquarters 0 BO - -
LS canarygrass0 - - - LS canarygrass 0 5 - -
Rape 1 0 10 55 30 Rape 1 5 0 20 20
Rape 2 - 25 20 50 Rape 2 - 10 0 20
Redroot pigweed60 - - - Redroot pigweed - 0 - -
Russian thistle- - - - Russian thistle - 20 - -
Scentless 70 - - - Scentless chamo - 60 - -
chamo
Speedwell 15 - - - Speedwell 0 - - -
Spring Barley0 20 - - Spring Barley 0 5 - -
Sugar beet 35 - - - Sugar beet 25 85 - -
Sunflower 0 - - - Sunflower o 30 - -
Veronica hedera- - - - Veronica hedera - 55 - -
Wheat - 4 - - Wheat - - - -
Wheat (spring)0 25 - - Wheat (spring) 0 10 - -
Wheat (winter)0 30 - - Wheat (winter) 0 5 - -
Wild buckwheat0 - - - Wild buckwheat o 10 - -
Wild mustard 50 80 68 100 Wild mustard 30 60 55
100
Wild oat 1 - - - - Wild oat 1 - 0 - -
Wild oat 2 0 30 - - Wild oat 2 0 - - -
Windgrass 0 - - - Windgrass 0 0 - -
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Table E COMPOUND Table E COMPOUND
Rate 4 g/ha 1 Rate 4 g/ha 1
POSTEMERGENCE POSTEMERGENCE
Annual bluegras 0 Rape 2 -
Barley (winter) 0 Redroot pigweed 30
Blackgrass 2 0 Russian thistle -
Blk nightshade 0 Scentless chamo 20
Chickweed 0 Speedwell 0
Common poppy - Spring Barley 0
Deadnettle 0 Sugar beet 15
Downy brome 0 Sunflower 0
Field violet 0 Veronica hedera -
Galium 2 0 Wheat -
Green foxtail 0 Wheat (spring) 0
I. Ryegrass 0 Wheat (winter) 0
Jointed goatgra 0 Wild buckwheat 0
Kochia 0 Wild mustard 30
Lambsquarters 0 Wild oat 1 -
LS canarygrass 0 Wild oat 2 0
Rape 1 0 Windgrass 0
TEST F
Plastic pots were partially filled with silt loam soil. The soil was then
saturated with
water. Indica Rice (Oryza sativa) seed (designated rice, indica 1 ) and
seedlings (designated
S rice, indica 3 ) at the 2 leaf stage, seeds, tubers or plant parts selected
from barnyardgrass
(Echinochloa crus-galli), ducksalad (Heteranthera limosa), early watergrass
(Echinochloa
oryzoides), junglerice (Echinochloa colonum), late watergrass (Echinochloa
oryzicola),
redstem (Ammania species), rice flatsedge (Cyperus iria), smallflower
flatsedge (Cyperus
difformis) and tighthead sprangletop (Leptochloa fasicularis), were planted
into this soil.
Plantings and waterings of these crops and weed species were adjusted to
produce plants of
appropriate size for the test. At the 2-leaf stage, water levels were raised
to 3 cm above the
soil surface and maintained at this level throughout the test. Chemical
treatments were
formulated in a non-phytotoxic solvent mixture which included a surfactant and
applied
directly to the paddy water by pipette, or to the plant foliage by an air
pressure-assisted,
calibrated belt-conveyer spray system.
Treated plants and controls were maintained in a greenhouse for approximately
21
days, after which all species were compared to controls and visually
evaluated. Plant
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response ratings, summarized in Table F, are reported on a 0 to l00 scale
where 0 is no effect
and l00 is complete control. A dash (-) response means no test result.
Table F COMPOUND Table F COMPOUND
Rate 200 g/ha4 Rate 150 g/ha 4
Paddy / silt Paddy / silt loam
loam
Barnyardgrass- Barnyardgrass -
Ducksalad 95 Ducksalad 95
E. watergrass- E. watergrass -
Junglerice - Junglerice -
L. watergrass- L. watergrass -
Redstem 95 Redstem 95
Rice flatsedge95 Rice flatsedge 95
Rice indica 100 Rice indica 1 90
1
Rice indica 70 Rice indica 3 65
3
S. flatsedge 98 S. flatsedge 98
T. sprangletop100 T. sprangletop 100
Table F COMPOUND Table F COMP OUND
Table
F
COMPOUND
Rate l25 g/ha2 4 5 Rate 100 g/ha 4 Rate 75 g/ha 4
Paddy / silt Paddy / silt loam Paddy / silt am
loam lo
Barnyardgrass0 - 60 Barnyardgrass - Barnyardgrass -
Ducksalad 98 95 90 Ducksalad 90 Ducksalad 95
E. watergrass- - 90 E. watergrass - E. watergrass -
Junglerice 100 - 65 Junglerice - Junglerice -
L. watergrass0 - 35 L. watergrass - L. watergrass -
Redstem 98 95 100 Redstem 90 Redstem 95
Rice flatsedge65 95 85 Rice flatsedge 85 Rice flatsedge85
Rice indica 15 90 40 Rice indica 1 65 Rice indica 50
1 1
Rice indica 10 70 45 Rice indica 3 55 Rice indica 45
3 3
S. flatsedge 100 95 85 S. flatsedge 95 S. flatsedge 95
T. sprangletop100 95 100 T. sprangletop l00 T. sprangletop100
Table F COMPOUND Table F COMPOUND Table F COMPOUND
Rate 64 g/ha 2 5 Rate 50 g/ha 4 Rate 32 g/ha 2 5
Paddy / silt loam Paddy / silt loam Paddy / silt loam
Barnyardgrass 0 15 Barnyardgrass - Barnyardgrass 0 0
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Ducksalad 98 90 Ducksalad 90 Ducksalad 60 85
E. watergrass - 35 E. watergrass - E. watergrass- 20
Junglerice 65 40 Junglerice - Junglerice 0 15
L. watergrass 0 20 L. watergrass - L. watergrass0 0
Redstem 98 100 Redstem 75 Redstem 50 75
Rice flatsedge 50 100 Rice flatsedge 80 Rice flatsedge10 65
Rice indica 1 10 30 Rice indica 10 Rice indica 0 25
1 1
Rice indica 3 10 20 Rice indica 10 Rice indica 0 10
3 3
S. flatsedge 100 100 S. flatsedge 90 S. flatsedge 100 65
T. sprangletop l00 98 T. sprangletop 65 T. sprangletop95 98
Table F COMPOUND Table F COMPOUND Table F COMPOUND
Rate 25 g/ha 4 Rate 16 g/ha 2 5 Rate 8 g/ha 2 5
Paddy / silt lo am Paddy / silt Paddy / silt
loam loam
Barnyardgrass - Barnyardgrass 0 0 Barnyardgrass0 0
Ducksalad 85 Ducksalad 55 45 Ducksalad 0 25
E. watergrass - E. watergrass - 15 E. watergrass- 0
Junglerice - Junglerice 0 0 Junglerice 0 0
L. watergrass - L. watergrass 0 0 L. watergrass0 0
Redstem 20 Redstem 40 55 Redstem 0 0
Rice flatsedge 65 Rice flatsedge 0 45 Rice flatsedge0 20
Rice indica 1 10 Rice indica 0 0 Rice indica 0 0
1 1
Rice indica 3 0 Rice indica 0 10 Rice indica 0 10
3 3
S. flatsedge 70 S) flatsedge 50 45 S. flatsedge 0 20
T. sprangletop 20 T. sprangletop 15 85 T. sprangletop0 85
