HERBICIDALLY ACTIVE 1,3,4-THIADIAZOLE DERIVATIVES

DERIVES DU 1,3,4-THIADIAZOLE, HERBICIDES

English Abstract

ABSTRACT OF THE INVENTION
Novel thiadiazole compounds have the general
structure:
<IMG>
wherein
R1 is hydrogen or a substituted or unsubstituted
lower acyclic hydrocarbon radical, the substituents
being selected from the class consisting of halo,
hydroxy, cyano, and lower alkoxy,
R2 is R1 or a lower alkoxy radical, except that R1
and R2 cannot both be hydrogen,
R3 is hydrogen or a lower acyclic hydrocarbon
radical,
R4 is hydrogen, a lower acyclic hydrocarbon
radical, or a lower cycloalkyl radical, and,
R5 is hydrogen, a lower cycloalkyl radical, a
lower alkoxy radical or a substituted or un-
substituted lower acyclic hydrocarbon radical,
the substituents being selected from the class
consisting of halo, hydroxy, cyano. or lower
alkoxy, except that R4 and R5 cannot both be
hydrogen or a lower cycloalkyl radical, and
metal or ammonium or substituted ammonium salts
thereof, are useful for their herbicidal activity
against a broad spectrum of undesiren weeds and
plants.

Claims

The embodiments of the invention in which an exclusive
property or privilege is claimed are defined as follows:-
1. A thiadiazole having the formula:
[A]
<IMG>
wherein
R1 is hydrogen or a substituted or unsubstituted lower
acyclic hydrocarbon radical, the substituents being
halo, hydroxy, cyano or lower alkoxy;
R2 is R1 or a lower alkoxy radical, with the proviso
that R1 and R2 cannot both be hydrogen;
R3 is hydrogen or a lower acyclic hydrocarbon radical;
R4 is hydrogen, a lower acyclic hydrocarbon radical,
or a lower cycloalkyl radical; and
R5 is hydrogen, a lower cycloalkyl radical, a lower
alkoxy radical, or a substituted or unsubstituted
lower acyclic hydrocarbon radical, the substituents
being halo, hydroxy, cyano, or lower alkoxy, with the
proviso that R4 and R5 cannot both be hydrogen or a
lower cycloalkyl radical; or
[B] a tautomer of [A], wherein R3 is hydrogen; or
[C] a metal or ammonium salt of [A] wherein R3 is
hydrogen;
but excluding the compounds wherein R1, R2, R3, R4
and R5 have the following definitions:
when R1 is methyl; R2, R3 and R4 are hydrogen and R5
is methyl;

when R1 is methyl; R2 is methoxy; R3 and R5 are methyl
and R4 is hydrogen;
when R1, R2 and R3 are ethyl; R4 is hydrogen and R5 is
methyl;
when R1 and R2 are ethyl; R3 and R5 are methyl and R4
is hydrogen;
when R1 and R2 are butyl, R3 and R4 are hydrogen and
R5 is methyl;
when R1 and R2 are allyl, R3 and R5 are methyl and R4
is hydrogen;
when R1, R3 and R5 are methyl and R2 and R4 are hydro-
gen; and
when R1 is methoxypropyl, R3 and R5 are methyl and R2
and R4 are hydrogen.
2. A thiadiazole having the formula:
[A] <IMG>
wherein
R1 is hydrogen or a substituted or unsubstituted lower
acyclic hydrocarbon radical, the substituents being
selected from the class consisting of halo, hydroxy,
cyano, and lower alkoxy,
R2 is R1 or a lower alkoxy radical, except that R1
and R2 cannot both be hydrogen,
R3 is hydrogen or a lower acyclic hydrocarbon radical,
26

R4 is hydrogen, a lower acyclic hydrocarbon radical,
or a lower cycloalkyl radical, and
R5 is hydrogen, a lower cycloalkyl radical, a lower
alkoxy radical, or a substituted or unsubstituted
lower acyclic hydrocarbon radical, the substituents
being selected from the class consisting of halo,
hydroxy, cyano, or lower alkoxy, except that R4 and
R5 cannot both be hydrogen or a lower cycloalkyl
radical, or
[B] a tautomer of [A] wherein R3 is hydrogen, but
excluding the compounds wherein R1, R2, R3, R4 and R5
have the following definitions:
when R1 is methyl; R2, R3 and R4 are hydrogen and R5
is methyl;
when R1 is methyl; R2 is methoxy; R3 and R5 are methyl
and R4 is hydrogen;
when R1, R2 and R3 are ethyl; R4 is hydrogen and R5
is methyl;
when R1 and R2 are ethyl; R3 and R5 are methyl and R4
is hydrogen;
when R1 and R2 are butyl, R3 and R4 are hydrogen and
R5 is methyl;
when R1 and R2 are allyl, R3 and R5 are methyl and R4
is hydrogen;
when R1, R3 and R5 are methyl and R2 and R4 are hydro-
gen; and
when R1 is methoxypropyl, R3 and R5 are methyl and R2
and R4 are hydrogen.
27

3. A thiadiazole having the formula:
<IMG>
wherein
R1 is hydrogen or a substituted or unsubstituted
lower acyclic hydrocarbon radical, the substituents
being selected from the class consisting of halo,
hydroxy, cyano and lower alkoxy,
R2 is R1 or a lower alkoxy radical, except that R1
and R2 cannot both be hydrogen,
R4 is hydrogen, a lower acyclic hydrocarbon radical,
or a lower cycloalkyl radical,
R5 is hydrogen, a lower cycloalkyl radical, a lower
alkoxy radical, or a substituted or unsubstituted
lower acyclic hydrocarbon radical, the substituents
being selected from the class consisting of halo,
hydroxy, cyano, or lower alkoxy, except that R4 and
R5 cannot both be hydrogen or a lower cycloalkyl ra-
dical,
Y is an alkali metal or ammonium radical, and
n is the chemical equivalence of Y,
but excluding the compounds wherein R1, R2, R4 and
R5 have the following definitions:
when R1 is methyl; R2 and R4 are hydrogen and R5 is
methyl; and
when R1 and R2 are butyl, R4 is hydrogen and R5 is
28

methyl.
4. The thiadiazole according to claim 1, which is 1-
methyl-3-(5-N,N-dimethylsulfamoyl-1,3,4-thiadiazol-2-yl)urea.
5. The thiadiazole according to claim 1, which is 1-
methyl-3-(5-N-butyl-N-methylsulfamoyl-1,3,4-thiadiazol-2-yl)-
urea.
6. The thiadiazole according to claim 1, which is 1-
methyl-3-(5-N-butylsulfamoyl-1,3,4-thiadiazol-2-yl)urea.
7. The thiadiazole according to claim 1, which is 1-
cyclopropyl-3-(5-N,N-dimethylsulfamoyl-1,3,4-thiadiazol-2-
yl)urea.
8. The thiadiazole according to claim 1, which is 1-
butyl-1-methyl-3-(5-N,N-dimethylsulfamoyl-1,3,4-thiadiazol-
2-yl)urea.
9. The thiadiazole according to claim 1, which is
1,3-dimethyl-3-(5-N,N-dimethylsulfamoyl-1,3,4-thiadiazol-2-
yl)urea.
10. The thiadiazole according to claim 1, which is
1-methyl-1-methoxy-3-(5-N,N-dimethylsulfamoyl-1,3,4-thia-
diazol-2-yl)urea.
11. The thiadiazole according to claim 1, which is
1-n-butyl-3-(5-N,N-dimethylsulfamoyl-1,3,4-thiadiazol-2-yl)-
urea.
12. The thiadiazole according to claim 1, which is
1,1-dimethyl-3-(5-N,N-dimethylsulfamoyl-1,3,4-thiadiazol-
2-yl)urea.
13. The thiadiazole according to claim 1, which is
29

1-methyl-3-(5-N-allylsulfamoyl-1,3,4-thiadiazol-2-yl)urea.
14. The thiadiazole according to claim 1, which is
1-methyl-3-(5-N,N-dipropylsulfamoyl-1,3,4-thiadiazol-2-yl)-
urea.
15. The thiadiazole according to claim 1, which is
1-methyl-3-(5-N-t-butylsulfamoyl-1,3,4-thiadiazol-2-yl)urea.
16. The thiadiazole according to claim 1, which is
1-methyl-3-[5-N-(1,1-dimethoxyethyl-2)-N-methylsulfamoyl-
1,3,4-thiadiazol-2-yl]urea.
17. The thiadiazole according to claim 1, which is
1-methyl-3-(5-N-chloroethylsulfamoyl-1,3,4-thiadiazol-2-yl)-
urea.
18. The thiadiazole according to claim 1, which is
1-methyl-3-(5-N-methoxy-N-methylsulfamoyl-1,3,4-thiadiazol-
2-yl)urea.
19. The thiadiazole according to claim 1, which is
1-methyl-3-[5-N-(1-methoxyisopropyl-2)-sulfamoyl-1,3,4-
thiadiazol-2-yl]urea.
20. The thiadiazole according to claim 1, which is
1,3-dimethyl-3-(5-N-cyanomethyl-N-methylsulfamoyl-1,3,4-
thiadiazol-2-yl)urea.
21. The thiadiazole according to claim 1, which is
1-methyl-3-(5-N-cyanomethyl-N-butylsulfamoyl-1,3,4-thiadia-
zol-2-yl)urea.
22. The thiadiazole according to claim 1, wherein
said metal salt is an alkali metal salt.
23. A method of controlling undesirable weeds and

plants which comprises applying to said weeds and plants a
herbicidally effective amount of a herbicidal composition
containing at least one thiadiazole having the formula:
[A]
<IMG>
wherein
R1 is hydrogen or a substituted or unsubstituted
lower acyclic hydrocarbon radical, the substituents
being halo, hydroxy, cyano or lower alkoxy;
R2 is R1 or a lower alkoxy radical, with the proviso
that R1 and R2 cannot both be hydrogen;
R3 is hydrogen or a lower acyclic hydrocarbon radical;
R4 is hydrogen, a lower acyclic hydrocarbon radical,
or a lower cycloalkyl radical; and
R5 is hydrogen, a lower cycloalkyl radical, a lower
alkoxy radical, or a substituted or unsubstituted
lower acyclic hydrocarbon radical, the substituents
being halo, hydroxy, cyano, or lower alkoxy, with the
proviso that R4 and R5 cannot both be hydrogen or a
lower cycloalkyl radical; or
[B] a tautomer of [A], wherein R3 is hydrogen; or
[C] a metal or an ammonium salt of [A] wherein R3 is
hydrogen;
but excluding the compounds wherein R1, R2, R3, R4
and R5 have the following definitions:
when R1 is methyl; R2, R3 and R4 are hydrogen and R5
is methyl;
when R1 is methyl; R2 is methoxy; R3 and R5 are methyl
31

and R4 is hydrogen;
when R1, R2 and R3 are ethyl; R4 is hydrogen and R5
is methyl;
when R1 and R2 are ethyl; R3 and R5 are methyl and R4
is hydrogen;
when R1 and R2 are butyl, R3 and R4 are hydrogen and
R5 is methyl;
when R1 and R2 are allyl, R3 and R5 are methyl and R4
is hydrogen;
when R1, R3 and R5 are methyl and R2 and R4 are hydro-
gen; and
when R1 is methoxypropyl, R3 and R5 are methyl and R2
and R4 are hydrogen;
as the active ingredient, and a carrier or diluent
therefor.
24. A method of controlling undesirable weeds and
plants which comprises applying to said weeds and plants a
herbicidally effective amount of a herbicidal composition
containing at least one thiadiazole having the formula:
[A]
<IMG>
wherein
R1 is hydrogen or a substituted or unsubstituted
lower acyclic hydrocarbon radical, the substituents
being selected from the class consisting of halo,
hydroxy, cyano, and lower alkoxy,
R2 is R1 or a lower alkoxy radical, except that R1
32

and R2 cannot both be hydrogen,
R3 is hydrogen or a lower acyclic hydrocarbon radical,
R4 is hydrogen, a lower acyclic hydrocarbon radical,
or a lower cycloalkyl radical, and
R5 is hydrogen, a lower cycloalkyl radical, a lower
alkoxy radical, or a substituted or unsubstituted
lower acyclic hydrocarbon radical, the substituents
being selected from the class consisting of halo, hy-
droxy, cyano, or lower alkoxy, except that R4 and R5
cannot both be hydrogen or a lower cycloalkyl radical;
or
[B] a tautomer of [A] wherein R3 is hydrogen;
but excluding the compounds wherein R1, R2, R3, R4
and R5 have the following definitions:
when R1 is methyl; R2, R3 and R4 are hydrogen and R5
is methyl;
when R1 is methyl; R2 is methoxy; R3 and R5 are methyl
and R4 is hydrogen;
when R1, R2 and R3 are ethyl; R4 is hydrogen and R5
is methyl;
when R1 and R2 are ethyl; R3 and R5 are methyl and R4
is hydrogen;
when R1 and R2 are butyl, R3 and R4 are hydrogen and
R5 is methyl;
when R1 and R2 are allyl, R3 and R5 are methyl and R4
is hydrogen;
when R1, R3 and R5 are methyl and R2 and R4 are hydro-
gen; and
33

when R1 is methoxypropyl, R3 and R5 are methyl and R2
and R4 are hydrogen;
as the active ingredient, and a carrier or diluent
therefor.
25. A method of controlling undesirable weeds and
plants which comprises applying to said weeds and plants a
herbicidally effective amount of a herbicidal composition
containing at least one thiadiazole having the formula:
<IMG>
wherein
R1 is hydrogen or a substituted or unsubstituted lower
acyclic hydrocarbon radical, the substituents being
selected from the class consisting of halo, hydroxy,
cyano, and lower alkoxy,
R2 is R1 or a lower alkoxy radical, except that R1
and R2 cannot both be hydrogen,
R4 is hydrogen, a lower acyclic hydrocarbon radical,
or a lower cycloalkyl radical,
R5 is hydrogen, a lower cycloalkyl radical, a lower
alkoxy radical, or a substituted or unsubstituted
lower acyclic hydrocarbon radical, the substituents
being selected from the class consisting of halo,
hydroxy, cyano, or lower alkoxy, except that R4 and
R5 cannot both be hydrogen or a lower cycloalkyl
radical,
Y is an alkali metal or ammonium radical, and
34

n is the chemical equivalent of Y,
but excluding the compounds wherein R1, R2, R4 and R5
have the following definitions:
when R1 is methyl; R2 and R4 are hydrogen and R5 is
methyl; and
when R1 and R2 are butyl, R4 is hydrogen and R5 is
methyl;
as the active ingredient, and a carrier or diluent
therefor.
26. The method according to claim 23, wherein the
metal salt is an alkali metal salt.
27. The method according to claim 23, wherein the
thiadiazole is 1-methyl-3-(5-N,N-dimethylsulfamoyl-1,3,4-
thiadiazol-2-yl)urea.
28. The method according to claim 23, wherein the
thiadiazole is 1-methyl-3-(5-N-butyl-N-methylsulfamoyl-
1,3,4-thiadiazol-2-yl)urea.
29. The method according to claim 23, wherein the
thiadiazole is 1-methyl-3-(5-N-butylsulfamoyl-1,3,4-thia-
diazol-2-yl)urea.
30. The method according to claim 23, wherein the
thiadiazole is 1-cyclopropyl-3-(5-N,N-dimethylsulfamoyl-
1,3,4-thiadiazol-2-yl)urea.
31. The method according to claim 23, wherein the
thiadiazole is 1-butyl-1-methyl-3-(5-N,N-dimethylsulfamoyl-
1,3,4-thiadiazol-2-yl)urea.
32. The method according to claim 23, wherein the

thiadiazole is 1,3-dimethyl-3-(5-N,N-dimethylsulfamoyl-1,3,4-
thiadiazol-2-yl)urea.
33. The method according to claim 23, wherein the
thiadiazole is 1-methyl-1-methoxy-3-(5-N,N-dimethylsulfamoyl-
1,3,4-thiadiazol-2-yl)urea.
34. The method according to claim 23, wherein the
thiadiazole is 1-n-butyl-3-(5-N,N-dimethylsulfamoyl-1,3,4-
thiadiazol-2-yl)urea.
35. The method according to claim 23, wherein the
thiadiazole is 1,1-dimethyl-3-(5-N,N-dimethylsulfamoyl-
1,3,4-thiadiazol-2-yl)urea.
36. The method according to claim 23, wherein the
thiadiazole is 1-methyl-3-(5-N-allylsulfamoyl-1,3,4-thia-
diazol-2-yl)urea.
37. The method according to claim 23, wherein the
thiadiazole is 1-methyl-3-(5-N,N-dipropylsulfamoyl-1,3,4-
thiadiazol-2-yl)urea.
38. The method according to claim 23, wherein the
thiadiazole is 1-methyl-3-(5-N-t-butylsulfamoyl-1,3,4-thia-
diazol-2-yl)urea.
39. The method according to claim 23, wherein the
thiadiazole is 1-methyl-3-[5-N-(1,1-dimethoxyethyl-2)-N-
methyl-sulfamoyl-1,3,4-thiadiazol-2-yl]urea.
40. The method according to claim 23, wherein the
thiadiazole is 1-methyl-3-(5-N-chloroethylsulfamoyl-1,3,4-
thiadiazol-2-yl)urea.
41. The method according to claim 23, wherein the
thiadiazole is 1-methyl-3-(5-N-methoxy-N-methylsulfamoyl-
1,3,4-thiadiazol-2-yl)urea.
36

42. The method according to claim 23, wherein the
thiadiazole is 1-methyl-3-[5-N-(1-methoxyisopropyl-2)-sulfa-
moyl-1,3,4-thiadiazol-2-yl]urea.
43. The method according to claim 23, wherein the
thiadiazole is 1,3-dimethyl-3-(5-N-cyanomethyl-N-methylsul-
famoyl-1,3,4-thiadiazol-2-yl)urea.
44. The method according to claim 23, wherein the
thiadiazole is 1-methyl-3-(5-N-cyanomethyl-N-butylsulfamoyl-
1,3,4-thiadiazol-2-yl)urea.
45. A thiadiazole having the formula:
[A] <IMG>
wherein R1 represents hydrogen, lower alkyl radical optionally
substituted by cyano or lower alkoxy, lower alkenyl and lower
alkynyl,
R2 is any of the moieties represented by R1,
R3 is hydrogen or lower alkyl of 1 to 2 carbon atoms,
R4 is hydrogen or lower alkyl,
R5 is hydrogen or lower alkyl with the proviso that
radicals R4 and R5 are not both hydrogen,
but excluding the compounds wherein R1, R2, R3, R4
and R5 have the following definitions:
when R1 is methyl; R2, R3 and R4 are hydrogen and R5
is methyl;
when R1 is methyl; R2 is methoxy; R3 and R5 are
methyl and R4 is hydrogen;
when R1, R2 and R3 are ethyl; R4 is hydrogen and R5
is methyl;
37

when R1 and R2 are ethyl; R3 and R5 are methyl and
R4 is hydrogen;
when R1 and R2 are butyl; R3 and R4 are hydrogen and
R5 is methyl;
when R1 and R2 are allyl; R3 and R5 are methyl and
R4 is hydrogen;
when R1, R3 and R5 are methyl and R2 and R4 are hy-
drogen; and
when R1 is methoxypropyl, R3 and R5 are methyl and
R2 and R4 are hydrogen.
46. A thiadiazole of Formula [A] in claim 45 wherein
R1 and R2 together with the nitrogen atom represent a mor-
pholine radical.
47. A thiadiazole having the formula:
[A] <IMG>
wherein R1 is hydrogen or alkyl of up to 3 carbon atoms or
allyl, R2 is any of the moieties represented by R1 or lower
alkoxy of up to 3 carbon atoms, R3 is hydrogen or methyl,
R4 is hydrogen or alkyl of up to 3 carbon atoms and R5 is
alkyl or alkoxy of up to 3 carbon atoms, but excluding the
compounds wherein R1, R2, R3, R4 and R5 have the following
definitions:
when R1 is methyl; R2, R3 and R4 are hydrogen and R5
is methyl;
when R1 is methyl; R2 is methoxy; R3 and R5 are methyl
38

and R4 is hydrogen;
when R1, R2 and R3 are ethyl; R4 is hydrogen and R5
is methyl;
when R1 and R2 are ethyl; R3 and R5 are methyl and R4
is hydrogen;
when R1 and R2 are butyl; R3 and R4 are hydrogen and
R5 is methyl;
when R1 and R2 are allyl, R3 and R5 are methyl and R4
is hydrogen;
when R1, R3 and R5 are methyl and R2 and R4 are hydro-
gen; and
when R1 is methoxypropyl, R3 and R5 are methyl and R2
and R4 are hydrogen.
48. The thiadiazole according to claim 46, which is
1-methyl-3-(5-morpholinosulfamoyl-1,3,4-thiadiazol-2-yl)urea .
49. The thiadiazole according to claim 45, which is
1-methyl-3-(5-sulfamoyl-1,3,4-thiadiazol-2-yl)urea.
50. The process of preparing a phytotoxic thiadiazole
having the Formula [A] in claim 45, the said process consist-
ing of reacting a compound of the formula:
<IMG>
with either
a) a carbamoyl chloride or an isocyanate of the for-
mula:
R4R5NCOCl or R5NCO
39

or
b) phosgene in an inert solvent, followed by reacting
the resulting carbamoyl chloride with an amine of the for-
mula:
R4R5NH
to yield said phytotoxic thiadiazole wherein R1, R2, R3, R4
and R5 are as defined in claim 45.
51. A process of preparing a phytotoxic thiadiazole
having the Formula [A] in claim 45, wherein R4 is hydrogen
which comprises reacting a compound of the formula:
<IMG>
with an isocyanate of the formula R5NCO wherein R5 is a lower
alkyl radical.
52. A process of preparing a phytotoxic thiadiazole
having the Formula [A] in claim 45 wherein R1 and R2 together
with the nitrogen atom represent the morpholine radical, the
said process consisting of reacting a compound of the formula:
<IMG>
with either
a) a carbamoyl chloride or an isocyanate of the for-
mula
R4R5NCOCl or R5NCO
or
b) phosgene in an inert solvent, followed by reacting
the resulting carbamoyl chloride with an amine of the for-

mula R4R5NH to yield said phytotoxic thiadiazole wherein R3,
R4 and R5 are as defined in claim 45.
53. A method of combatting unwanted vegetation by
applying to a locus containing unwanted vegetation or sus-
ceptible to the growth of unwanted vegetation an effective
amount of a thiadiazole having the Formula [A] as defined in
claim 45.
54. A method of combatting unwanted vegetation by
applying to a locus containing unwanted vegetation or sus-
ceptible to the growth of unwanted vegetation an effective
amount of a thiadiazole having the Formula [A] of claim 45
wherein radicals R1 and R2 together with the nitrogen atom
represent a morpholine radical.
55. A method of combatting unwanted vegetation by
applying to a locus containing unwanted vegetation or sus-
ceptible to the growth of unwanted vegetation an effective
amount of a thiadiazole having the Formula [A] as defined
in claim 47.
56. A method of combatting unwanted vegetation by
applying to a locus containing unwanted vegetation or sus-
ceptible to the growth of unwanted vegetation an effective
amount of the thiadiazole, 1-methyl-3-(5-N,N-dimethylsulfa-
moyl-1,3,4-thiadiazol-2-yl)urea.
57. A method of combatting unwanted vegetation by
applying to a locus containing unwanted vegetation or sus-
ceptible to the growth of unwanted vegetation an effective
amount of the thiadiazole, 1,3-dimethyl-3-(5-N,N-dimethyl-
sulfamoyl-1,3,4-thiadiazol-2-yl)urea.
58. A method of combatting unwanted vegetation by
41

applying to a locus containing unwanted vegetation or sus-
ceptible to the growth of unwanted vegetation an effective
amount of the thiadiazole, 1-methyl-1-methoxy-3-(5-N,N-di-
methylsulfamoyl-1,3,4-thiadiazol-2-yl)urea.
59. A method of combatting unwanted vegetation by
applying to a locus containing unwanted vegetation or sus-
ceptible to the growth of unwanted vegetation an effective
amount of the thiadiazole, 1-methyl-3-(5-N-butylsulfamoyl-
1,3,4-thiadiazol-2-yl)urea.
60. A method of combatting unwanted vegetation by
applying to a locus containing unwanted vegetation or sus-
ceptible to the growth of unwanted vegetation an effective
amount of the thiadiazole, 1-methyl-3-(5-morpholinosulfa-
moyl-1,3,4-thiadiazol-2-yl)urea.
61. A method of combatting unwanted vegetation by
applying to a locus containing unwanted vegetation or sus-
ceptible to the growth of unwanted vegetation an effective
amount of the thiadiazole, 1-n-butyl-3-(5-N,N-dimethylsul-
famoyl-1,3,4-thiadiazol-2-yl)urea.
62. A method of combatting unwanted vegetation by
applying to a locus containing unwanted vegetation or sus-
ceptible to the growth of unwanted vegetation an effective
amount of the thiadiazole, 1,1-dimethyl-3-(5-N,N-dimethyl-
sulfamoyl-1,3,4-thiadiazol-2-yl)urea.
63. A method of combatting unwanted vegetation by
applying to a locus containing unwanted vegetation or sus-
ceptible to the growth of unwanted vegetation an effective
amount of the thiadiazole, 1-methyl-3-(5-N-allylsulfamoyl-
1,3,4-thiadiazol-2-yl)urea.
42

64. A method of combatting unwanted vegetation by
applying to a locus containing unwanted vegetation or sus-
ceptible to the growth of unwanted vegetation an effective
amount of the thiadiazole, 1-methyl-3-(5-N,N-di-n-propylsul-
famoyl-1,3,4-thiadiazol-2-yl)urea.
65. A method of combatting unwanted vegetation by
applying to a locus containing unwanted vegetation or sus-
ceptible to the growth of unwanted vegetation an effective
amount of the thiadiazole, 1-methyl-3-(5-N-t-butylsulfamoyl-
1,3,4-thiadiazol-2-yl)urea.
66. A method of combatting unwanted vegetation by
applying to a locus containing unwanted vegetation or sus-
ceptible to the growth of unwanted vegetation an effective
amount of the thiadiazole, 1-methyl-3-(5-sulfamoyl-1,3,4-
thiadiazol-2-yl)urea.
67. A thiadiazole of the formula [A] in claim 45
wherein
R1 is hydrogen, lower alkyl or lower alkenyl,
R2 is any of the moieties represented by R1,
R3 is hydrogen or lower alkyl of 1 to 2 carbon atoms,
R4 is hydrogen or lower alkyl, and
R5 is hydrogen, lower alkyl or lower cycloalkyl
wherein R4 and R5 are not both hydrogen.
68. A method of combatting unwanted vegetation by
applying to a locus containing unwanted vegetation or sus-
ceptible to the growth of unwanted vegetation an effective
amount of a thiadiazole having the Formula [A] of claim 45
as defined in claim 67.
69. A thiadiazole according to claim l wherein R1
and R2 are independently C1-C4 alkyl, optionally substituted
43

with halo, hydroxy, cyano or C1-C2 alkoxy;
R3 and R4 are independently hydrogen or C1-C2 alkyl;
R5 is C1-C2 alkyl;
provided that R1 and R2 are not both ethyl or both butyl.
70. A thiadiazole according to claim 69 wherein R3
is C1-C2 alkyl.
71. A thiadiazole according to claim 70 wherein R1
and R2 are independently C1-C4 alkyl.
72. A method according to claim 23, wherein, in the
thiadiazole, R1 and R2 are independent C1-C4 alkyl, option-
ally substituted with halo, hydroxy, cyano or C1-C2 alkoxy;
R3 and R4 are independently hydrogen or C1-C2 alkyl;
R5 is C1-C2 alkyl;
provided that R1 and R2 are not both ethyl or both butyl.
73. A method according to claim 72 wherein, in the
thiadiazole, R3 is C1-C2 alkyl.
74. A method according to claim 73 wherein, in the
thiadiazole, R1 and R2 are independently C1-C4 alkyl.
75. A process of preparing a thiadiazole of claim 69,
which comprises reacting a compound of the formula:
<IMG>
with either
a) a carbamoyl chloride of an isocyanate having the
formula
R4R5NCOCl or R5NCO
44

b) phosgene in an inert solvent, followed by reacting
the resulting carbamoyl chloride with an amine of the for-
mula R4R5NH to yield said thiadiazole, wherein R1, R2, R3,
R4 and R5 are defined as in claim 69.
76. The process according to claim 75, wherein R3 is
C1-C2 alkyl.
77. The process according to claim 76, wherein R1
and R2 are independently C1-C4 alkyl.
78. A method of combatting unwanted vegetation by
applying to a locus containing unwanted vegetation or sus-
ceptible to the growth of unwanted vegetation, an effective
amount of a thiadiazole as defined in claim 69.
79. The method according to claim 78 wherein, in the
thiadiazole, R3 is C1-C2 alkyl.
80. The method according to claim 79, wherein, in the
thiadiazole, R1 and R2 are independently C1-C4 alkyl.

Description

'i~5..~3~
The invention pertains to thiadiazoles and
derivatives thereof which have utility as agricultural
pesticides. The thiadiazoles may be represented
most broadly, as having the structure:
RlR2NS02 ~ NR R
wherein
Rl is hydrogen or a substituted or unsubstituted
lower acyclic hydrocarbon radical, the substituents
being selected from the class consisting of halo,
hydroxy, cyano, and lower alkoxy,
R2 is Rl or a lower alkoxy radical, except that
Rl and R2 cannot both be hydrogen,
R3 is hydrogen or a lower acyclic hydrocarbon
radical,
R4 is hydrogen, a lower acyclic hydrocarbon
radical, or a lower cycloalkyl radical, and,
R5 is hydrogen, a lower cycloalkyl radical, a
lower alkoxy radical or a substituted or un-
substituted lower acyclic hydrocarbon radical,
the substituents being selected from the class
consisting of halo, hydroxy, cyano, or lower
alkoxy, except that R4 and R5 cannot both be
hydrogen or a lower cycloalkyl radical.
. . ~ :, . ., . . ~, .

~B~'7
The terms "lower acyclic hydrocarbon radical", lower
cycloalkyl radical", and "lower alkoxy radical" are
intended to mean such radicals containing up to seven
carbon atoms.
It is to be understood that in Structure (I)
above, where R3 is hydrogen, it may exist in the
tautomeric form:
] ~ ~ a H
RlR2NS2 ~ S ~ _ NCONR4R5
where Rl, R2, R4, and R5 have the designations hereinbefore
set forth. Therefore, in compositions of the invention
where R3 is hydrogen, the above tautomeric structure is
always implied to exist.
Y 1' R2, R3, R4, and R5 will have the
same meaning throughout the entirety of the specification
and claims.
The compounds show excellent activity as agricultural
pesticides, particularly as herbicides, for controlling a
broad spectrum of unwanted and undesirable weeks and plants.
Preferred Embodiments of the Invention
Methods of Synthesis
Generally, the compounds of the present invention
may be prepared by one or more of the synthesis routes set
forth below. The type of product desired will determine
the particular synthesis route to be employed.
'"`

8~7
HN N HN- N
CH3COC~ 3 (II)
S ~ S ~ NH 3 (or) CH3COOH S~ ~ NCOCH3
l C12
HN _ N ~ ~ 13
NCONR4R5 ClSO2 NCOCH3
C12 1 RlR2NH
(VII) I l R3 N -N R
ClSO2 ~ ~ CONR4 5 1 2 2 NCOCH3
1 RlR2NH ¦ HCl
N N N N (V~
~ 2 2 ~ S ~ 4 5 RlR2NSO2 ~ ~ NHR3
RlR2N602 ~ ~ NHCONR4R5 (i) KOH RlR2NSO2 ~ ~ NCONR4R5
S(ii) R3X
NaOH/I2 / - R
(I) > ~ _ ~ . ~¦ ~ 13
t S S N3R3 / - 3 -5 ~ i ~ NCONR4
(VII)

8~357
The designations for Rl through R5 have been pre-
viously described and the method of synthesis of any of the
above-described compounds is dependent upon the desired
compound.
Generally, the compound corresponding to formula
(I) are known; however, others are prepared by standard
methods. The 5-acetamido-1,3,4-thiadiazoles (II) utilized
are prepared by known methods from (I) and the corresponding
sulfonyl chlorides (III) are also prepared by known methods.
A particularly useful method is that of Petrow et al. (J.Chem.
Soc. 1508, 1958). The sulfonamides (IV) are prepared by the
reaction of the sulfonyl chlorides with primary or secondary
amines in aqueous or non-aqueous solutions at temperatures
of 0-60C, preferably in the range 0-10C. For non-aqueous
reactions inert solvents such as benzene, halogenated hydro-
carbons, tetrahydrofuran and the like can be used. The 2-
amino-5-sulfonamido-1,3,4-thiadiazoles (V) are obtained by
the treatment of compounds (IV) with concentrated hydro-
chloric acid according to the method of Petrow et al.
(loc. cit.).
A number of 2-ureido-1,3,4-thiadiazole sulfonyl
chLorides (VII) and 2-ureido-1,3,4-thiadiazole sulfonamides
(VIII) are prepared by methods similar to those employed
to produce compounds (III) and (IV).
Other ureido compounds may be derived from compound
(V) according to a variety of methods which are used for
the preparation of such compounds and which are well docu~ented
in the chemical litera~re. For ex~le, c~x~nds of Structure ~ may
.
,..

8~S7
be reacted with isocyanates in an inert solvent
such as benzene, dimethylformamide, ethyl acetate
and the like. A catalyst such as triethylamine may
be employed for this reaction.
52 ~ ~1 ~ + ~CO ~ ~R2~S2 -~ ~
Another reaction which may be employed is that
in which a carbamoyl chloride is reacted with an
amine in the presence of an acid fixing compound such
as sodium carbonate, triethylamlne, pyridine and the
like. Another variation of this reaction is the
reaction of a metal derivative of an amine with a
carbamoyl chloride. Inert solvents such as benzene,
tetrahydrofuran, dimethyl formamide, dioxane and
the like may be used to carry out the above reaction.
N _ N
2 ~ ClOONR4~N N
S RlS2~02 ~S~/ ~;E~R5
RlR2NS2~ r~o~4l
X = Na, K or Li
-- 6 --
:- . - ''

57
A further reaction which may be employed is
that in which NN'-carbonyldiimidazole is reacted with
an aminothiadiazole to give an intermediate isocyanate
which is then further reacted with an amine to produce
the desired product.
Q ~ R,
O~ NSO~ ~JUL ~ S 2J~5/L ~ ¦
~50 ~ ~ ~HCO~ R~RSNH ~ 50 ~ ~ ~CO + H~F ¦
Phosgene may also be reacted with an amine to
give a carbamoyl chloride which is then further reacted
with a primary or secondary amine to produce the desired
urea product. This reaction may be carried out in the
presence of a base, e.g., tertiary amine, and/or a
catalyst such as boron trifluride-ether complex. These
reactions can also be carried out in inert solvents
such as aromatic hydrocarbons, dimethyl formamide,
tetrahydrofuran and the like.
~ ~ N 50~ 3 ~ co 1~ / 5 ~s~
' ¦ R~RSIV~
~so,~ rJcO~ qR5

57
The ureas of the invention which correspond
to the generic formula (IX) will form metal or am-
monium salts (substituted or unsubstituted) corres-
ponding to structure (X). For polyvalent metals,
these salts are chelate in character. The alkali metal
and ammonium salts also possess the highly desirable
property, for agricultural applications, of being
water soluble. Furthermore, alkali metal salts are
found to react with reactive halogen compounds, e.g.,
alkyl halides, to produce derivatives as shown in (XI)
and (XII) below:
N
lR2N5 ~ l ~ HCONR4R5 (IX)
' N - N ~
Y = metal or ammonium radical ~.
n = equivalence of Y
N N
~`~ ~ N50 ~ S ~ 1CONR4
N - Nl ~
N5 2 5 ~ NOONR4R5
(XII)
-- 8 --

8~57
The following examples are illustrative of the
invention and are not intended to limit the scope thereof.
~thesis of Intermediates
Example 1
__
To a well stirred mixture containing 231 gms of
polyphosphoric acid and 488 gms of acetic acid and heated
to 100C was added 300 gms of 2-amino-5-mercapto-1,3,4-
thiadiazole. Upon complete addition of the thiadiazole,
the mixture was stirred for an additional l hour at 120C.
The mixture was cooled to 60C and poured into ice water
to provide a solid residue which was subsequently separated
by filtering. The residue was dissolved in 10% sodium
hydroxide (the small amount of insolubles being removed by
filtering) and the solution being adjusted to pH of 1 with
6N hydrochloric acid. The solid product was identified to
be 2-acetamido-5-mercapto-1,3,4-thiadiazole having a melting
point of 293 - 294C.
Example 2
One hundred fifty grams of 2-acetamido-5-mércapto-
1,3,4-thiadiazole was suspended in 3.5 litres of 70% acetic
acid and cooled to a temperature of 0-5C. A stream of
chlorine gas was slowly bubbled through the cooled mixture
at the above temperature for about 2 hours with vigorous
stirring. The solids were separated by filtering, washed
with ice water and air dried. The solid product was identi-
fied to be 2-acetamido-S-chlorosulfonyl-1,3,4-thiadiazole
having a melting point of 237-239C.
Example 3
Two hundred fifty mls of a 40% solution of aqueous
dimethylamine was added to 168.5gms of 2-acetamido-5-chlorosulfonyl-

1,3,4-thiadiazole while maintaining the termpature below
20C. After stirring the mixture for about 4 hours, the
mixture was acidified with 6N hydrochloric acid, the
solids separated by filtration and washed thoroughly with
water. The solid product was identified to be 2-acetamido-
5-NN-dimethylsulfonamido-1,3,4-thiadiazole having a melting
point of 258 - 260C.
Example 4
' A mixture containing 181.6 gms of 2-acetamido-
1,3,4-thiadiazole-5-NN-dimethylsulfonamide and 1000 mls
of concentrated hydrochloric acid was refluxed for about
3 1/2 hours. The mixture was cooled to room temperature,
filtered and the filtrate concentrated to dryness under
vacuum. The solid residue was admixed with 200 mls of 10%
aqueous sodium carbonate and filtered. The resulting solid
residue was identified to be 2-amino-1,3,4-thiadiazole-5-NN-
dimethylsulfonamide and having a melting point of 184-
186C.
~xample 5
A mixture containing 8.0 gms of 2-amino-5-mercapto-
1,3,4-thiadiazole, 3.4 gms of methylisocyanate and 150 mls
of NN-dimethylformamide was heated to 50C for about 1 hour.
The reaction mixture was concentrated under vacuum and
ice water subsequently added to the concentrate. The
solid residue was separated by filtration and identified
to be l-methyl-3-(S-mercapto-1,3,4-thiadiazole-2-yl)urea
having a melting point of 234C.
- 10 -
' :

~ ~ ~ 8',~7
Example 6
Sixty gms of l-methyl-3-(5-mercapto-1,3,4-
thiadiazole-2-yl) urea was suspended in 1.32 litres of
70% acetic acid, the mixture being formed in a flask
equipped with a mechanical stirring means. The mixture
was cooled to about 5C and chlorine gas slowly bubbled
through for about 45 minutes while maintaining the 5C
temperature. The resulting solids were separated by
filtration, washed with water and air dried. The product
was identified to be l-methyl-3-(5-chlorosulfonyl-1,3,4-
thiadiazole-2-yl)urea having a melting point of 141C.
Synthesis of Final Products
Example 7
Twenty gms of l-methyl-3-(5-chlorosulfonyl-1,3,4-
thiadiazol-2-yl)urea was dissolved, with stirring, in 250
mls of a 40% aqueous solution of methylamine while maintaining
the temperature of the reaction from about 5 - 7C. After
stirring for an additional 1-1/2 hours, the mixture was
acidified to pH 1 with 6N hydrochloric acid, the solids
separated by filtration and subsequently washed with water.
The final product was identified to be l-methyl-3-(5-N-
methylsulfamoyl-1,3,4-thiadiazol-2-yl)urea having a melting
point of 232 - 233C.
Example 8
A mixture containing 4.1 gms of 2-amino-1,3,4-
thiadiazole-5-NN-dimethylsulfonamide and 1.3 gms of
methylisocyanate was refluxed in anhydrous benzene for 3 hours. The
- 11 -
:;
,~
~ ~ ,
.

~ 5 ~
mixture was cooled to 10C, the solid product separated
by filtration and subsequently crystallized from ethanol.
The final product was identified to be l-methyl-3-(5-NN-
dimethylsulfamoyl-1,3,4-thiadiazol-2-yl)urea having a
melting point of 223- 23~C.
Example 9
A mixture containing 18.0gms of 2-amino-1,3,4-
thiadiazole-5-(N-methyl-N-butyl)sulfonamide, 5.4 gms of
methylisocyanate and 300 mls of anhydrous dimethylformamide
was heated to and maintained at 50C for about 1 hours.
The dimethylformamide was removed under vacuum and the solid
residue crystallized from solox. The final product was
ldentified to be l-methyl-3-(5-N-butyl-N-methylsulfamoyl-l,
3,4-thiadiazol-2-yl)urea having a melting point of 192-
193C
Example 10
The procedure of Example 9 was substantially re-
peated except that 13.8 gms of 2-amino-1,3,4-thiadiazole-5-
butylsulfonamide, 4.3 gms of methylisocyanate and 250 mls
of anhydrous dimethylformamide were employed. The final
product was identified to be l-methyl-(5-N-butylsulfamoyl-
1,3,4-thiadiazol-2-yl)urea having a melting point of
186 - 187C.
Example 11
A mixture containing 28.2 gms of 2-amino-1,3,4-
thiadiazole-5-NN-dimethylsulfonamide, and 12.5 gms cyclo-
propylisocyanate and 400 nls of anhydrous dimethylform~de was heated to and
- 12 -
7'

maintained at 50C for about 1 hour. The dimethylform-
amide was removed under vacuum, leaving a solid residue
which was crystallized from methanol. The final product
was identified to be l-cyclopropyl-3-(5-NN-dimethyl-
sulfamoyl-1,3,4-thiadiazol-2-yl)urea having a melting point
of 216C.
Example 12
A mixture containing 20 gms of 2-amino-5-morpholino-
sulfonyl-1,3,4-thiadiazole, 6.0 gms of methylisocyanate and
200 mls of anhydrous dimethylformamide was heated to and
maintained at 50C for about 1 hour. The dimethylformamide
was removed under vacuum and the solid residue crystallized
from a benezenemethanol mixture. The resulting product was
identified to be l-methyl-3-(5-morpholinosulfonyl-1,3,4-
thiadiazol-2-yl)urea having a melting point of 245-246C.
~xample 13
To amixture containing 28.2 gms of 2-amino-1,3,
4-thiadiazole-5-NN-dimethylsulfonamide and 18.4 gms of N
butyl-N-methyl carbamoyl chloride in 150 mls of anhydrous
tetrahydrofuran, was added in small portions, 4.7 gms of
sodium hydride. The reaction mixture was stirred for
1 1/2 hours, water added and the mixture subsequently
extracted with ethyl acetate. The ethyl acetate solution
was dried over anhydrous sodium sulfate and concentrated
under vacuum. The solid residue was crystallized from
ethyl acetate. The final product was identified to be
l-butyl-l-methyl-3-(5-NN-dimethylsulfamoyl-1,3,4-thiadiazol-
2-yl)urea having a melting point of 163 - 165C.
- 13 -
~' .
.,
., . : .

E ~mple 14
To a mixture containing 100 mls of methanol, and
10 gms 1-methyl-3-(5-NNdimethylsulfamoyl-1,3,4-thiadiazol-
2-yl)urea was added 2.4 gms of potassium hydroxide and 5.4
gms of methyl iodide, the entire mixture being refluxed for
30 minutes. The solids were separated by filtration and
the filtrate concentrated under vacuum to provide a solid
residue. The residue was recrystallized from methanol.
The final product was identified to be 1,3-dimethyl-3-
(5-NN-dimethylsulfamoyl-1,3,4-thiadiazol-2-yl)urea having
a melting point of 209-212C.
Example 15
To a mixture of 6 gms of NN'-carbonyldiimidazole
in dry tetrahydrofuran, under an atmosphere of nitrogen, was
added 3.5 gms of 2-amino-1,3,4-thiadiazole-5-NN-dimethyl-
sulfonamide. The mixture was stirred at room temperature
for 30 minutes and subsequently refluxed for about 15
minutes. The reaction mixture was cooled to room tempera-
ture and 5.6 gms of triethylamine and 5.4 gms of N,0-dim-
ethylhydroxylamine hydrochloride were added. The resulting
mixture was stirred for about 15 minutes after which the
mixture was poured into ice water. The solid residue was
separated by filtering and theresidue subsequently
crystallized from methanol. The final product was identi-
fied to be l-methyl-l-methoxy-3-(5-NN-dimethylsulfamoyl-
1,3,4,-thiadiazol-2-yl)urea having a melting point of
147 - 149C.
Additional compounds of the invention were pre-
pared in accordance with the procedures set forth above.
- 14 -

~ ~*~ ~ 7
Example Rl R2 Ra R4 R5 Melting Point,
16 CH3 CH3 H H CH3CH2CH2CH2 213-215
17 CH3 CH3 H ~H~ CH3 187-189
18 CH2=CHCH2 H H H GH3 166-168
19 C3H7 C3~ H H CH3 158-159
E~le 20
To a stirred suspension of 80 gms of 5-methylamino-
2-mercapto-1,3,4-thiadiazole in 300 mls of methanol was added,
in small portions, 26 gms of sodium hydroxide. The stirring
was continued until a complete solution was obtained (a small
amount of insoluble material being removed by filtration).
Iodine (66.4 gms) dissolved in 350 mls of methanol was next
added drop-wise to the above stirred solution. A yellow
precipitate began to separate after approximately half of the
iodine solution had been added. After complete addition of
the iodine solution the solids were filtered off and washed
with a little methanol to give the desired di-5-(methylamino-
1,3,4-thiadiazolyl) disulfide (XIII, R3= CH3) having a
melting point of 202-204C.
Example 21
A mixture containing 4 gms of di-5-(2-methyl-
amino-1,3,4-thiadiazolyl) disulfide, 1.6 gms of methyliso-
cyanate, and 20 mls of NN-dimethylformamide was heated at
100C for 1.75 hours. Water was next added to the reaction mix-
ture until a precipitate appeared. Thetotal solids which pre-
cipitated on further cooling were removed by filtration
and were washed thoroughly with water.
- 15 -
...
.. . . . .
.

o57
The resulting product was identified to be die-5-[1,
3-dimethyl-3-(1,3,4-thiadiazol-2-yl)urea]disulfide
(XIV, R4= H; ~3= R5 = CH3) having a meIting point of
219-221C.
Example 22
Four gms of di-5-[1,3-dimethyl-3-(1,3,4-
thiadiazol-2-yl)urea] disulfide was suspended in 120 mls of
70% acetic acid, the mixture being formed in a flask with
mechanical stirring means. The mixture was cooled to about
10C and chlorine gas slowly bubbled through for 1 hour
while maintaining a temperature range of 10-15C. After
approximately 30 minutes, the reaction mixture became clear.
The reaction mixture was next diluted with water and ex-
tracted with chIoroform. The chloroform solution was washed
with water, dried (Na2SO4) and concentrated under vacuum to
give the desired 1,3-dimethyl-3-(5-chlorosulfonyl-1,3,4-
thiadiazole-2-yl)urea having a melting point of 9~-100C
(dec).
Example 23
To a stirred mixture containing 1.5 gms of 1,3-
dimethyl-3-(5-chlorosulfonyl-1,3,4-thiadiazol-2-yl)urea and
; 0.5 gms of dimethylhydroxylamine hydrochloride in 20 mls of
tetrahydrofuran was added, dropwise, 1.0 gms of triethylamine
` in 5 mls of tetrahydrofuran and the reaction mixture stirred
overnight at room temperature. The reaction mixture was
next filtered and the filtrate concentrated under vacuum
to a solid residue. This solid was dissolved in ethyl acetate,
washed successively with dilute hydrochloric acid and
water, dried (Na2SO4) and concentrated under vacuum.
The residual solid was crystallized from aqueous
~r
i~ - 16 -

~ 8~ ~ 7
methanol. The final product was identified to be 1,3-
dimethyl-3~5-(N-methoxy-N-methyl)sulfamoyl-1,3,4-thiadiazol-
2-yl]urea having a melting point of 190 - 192C.
The following additional compounds of the in-
vention were prepared using the above procedures.
E~m,ple ~ R2 R3 , R,4 R5 ~llOting Point,
~4C( ~ )3 H H H 'CH3 247-249
2 ~X~
S CH3 CH2CH~ ~ H H CH3 156-158
26 H H H H CH3 245-247 (dec)
27ClCH2CH2 H H H CH3 197-199
28 CH3 ~ H H CH3 167-169
29C~CHC~ ~ H H H CH3 174-176
30C~CN CH3 CH3 H CH3 200-202
31C~CN C4Hg H H CH3 127-130
Biolog'ical Activity of Fin'al Products
The herbicidal activity of products of the in-
vention were tested in accordance with the procedure herein-
after set forth. For pre-emergence testing the soil in which
seeds were planted, was sprayed the same day with a solution
containing the designated amount of product in a 50-100%
acetone-water mixture. Observations of activity were
recorded twenty-one (21) to twenty-eight (28) days after
planting and spraying. For post-emergence testing, the
plants were sprayed with the same solution as described
above about fourteen (14) days after planting of the seeds.
A vigor and kill rating was adopted to assess the phytotoxicant properties
of the products. For both testing procedures a percent kill rating
- 17 -
. - . ., , ~ - ,

~ t~7
for each species of plants was obtained by comparing the
stand of treated plantings with untreated control plants
growing under similar conditions. A vigor rating of 1
to 5 was given to those plants not killed by chemical
treatment and is defined as follows:
1. severe injury, plants will die.
2. moderate-to-severe injury, plants are not
expected to recover from chemical treatment.
3. moderate injury, plants are expected to show
various degrees of recovery from chemical
treatment.
4. slight injury, plants will or have recovered
and will resume normal growth.
5. no apparent injury
The following tables show the pre- and post-emergence
herbicidal activity of compounds of the invention.
- 18 -
.. .
,~

The evaluated plant species are identified below
as to their corresponding Latin names:
Sugar Beets: Beta vulgaris
Corn: Zea mays
Oats: Avena sativa
Clover: Melilotus indica
Soybeans: Glycine max
Cotton: Gossypium hirsutum
Mustard: Brassica juncea
Yellow Foxtail: Setaria lauca
Barnyardgrass: Echinochloa crusgalli
Crabgrass: Digitaria sanguinalis
Buckwheat: Fagopyrum tataricum
Morningglory: Ipomoca purpurca
Pigweed: Amaranthus retroflexus
Jimsonweed: Datura stramonium
- 19 -
~ .
i,. i,.
: . .

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:~ :

~r~ 7
When utilized for herbicidal purposes, compounds
of the invention may be formulated in a variety of ways
and concentrations for application to the locus of desired
vegetation control. It is recognized that the particular
type and concentration of formulation, as well as the mode
of application of the active ingredient, may govern its
biological activity in a given application.
Compounds of the invention may be prepared as
simple solutions of the active ingredient in an appropriate
solvent in which it is completely soluble at the desired
concentration. Such solvent systems include water, al-
cohols, acetone, aqueous alcohol and acetone, and other
organic solvents. These simple solutions may be further
modified by the addition of various surfactants, emulsi-
fying or dispersing agents, colorants, odorants, anti-
foaming agents, other herbicides or herbicidal oils which
supplement or synergize the activity of the herbicides of
the invention, or other adjuvants for any given application
where deemed desirable to impart a particular type or
degree of plant responses.
Compounds of the invention may also be formulated
in various types of formulations commonly recognized by
those skilled in the art of agricultural or industrial
chemicals. These formulations include, for example,
compositions containing the active ingredient as granules
of relatively large particle size, as powder dusts, as
wettable powders, as emulsifiable concentrates or as a
constituent part of any other known type of formulation
commonly utilized by those skilled in the art. Such fora,ulations
inlclude the adjuvants and carriers normally employed for
facilitating the dispersion of active ingredientfor a~ricultral and
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industrial applications of phytotoxicants. These formula-
tions may contain as little as 0,25% or more than 95% by
wei.ght of the active ingredient.
Dust formulations are prepared by mixing the active
ingredient with finely divided solids which act as dis-
persants and carriers for the phytotoxicant in applying it
to the locus of application for vegetation control~ Typical
solids which may be utilized in preparing dust formulations
of the active ingredients of the invention include talc,
kieselguhr, finely divided clay, fullers' earth, or other
common organic or inorganic soli~s. Solids utilized in
preparing dust formulations of the active ingredient
normally have a particle size of 50 microns or les~. The
active ingredient of these dust formulations i8 present
commonly from as little as 0.25% to as much as 30% or more ~ -
by weight of the composition.
Granular formulations of the active ingredients
are prepared by impregnating or adsorbing the toxicant
on or into rleatively coarse particles of inert solids such
as sand, attapulgite clay, gypsum, corn cobs or other in-
organic or organic solids. The active ingredient of these
granular formulations is commonly present from 1.0% to
as much as 20. OV/D or more by weight of the composition.
Wettable powder formulations are solid compositions
of matter wherein the active ingredient is absorbed or
adsorbed in or on a sorptive carrier such as finely divided
clay, talc, gypsum, lime, wood flour, fullers' earth,
kieselguhr or the like. These formulations prefer-
ably are made t~ contain 50% to 80% of active
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''' ~ ' ~ .

~ i5~
ingredient. These wettable powder formulations commonly
contain a small amount of a wetting, dispersing or emulsi-
fying agent to facilitate dispersion in water or other
liquid carrier utilized to distribute the phytotoxicant
to the locus of desired vegetation control.
Emulsifiable concentrate formulations are homo-
geneous liquid or paste compositions containing the active
ingredient which will disperse in water or other liquid
carrier to facilitate application of the phytotoxicant
to the locus of desired vegetation control. Such emulsi-
fiable concentrate formulations of the active ingredients
may contain only the active ingredient with a liquid or
solid emulsifying agent or may contain other relatively
non-volatile organic solvents such as isophorone, dioxane,
heavy aromatic naphthas, xylene, or dimethyl formamide.
The active ingredient in such formulations commonly com-
prises 10.0% to 70.0% by weight of the phytotoxicant
composition.
In place of the particular compositions employed
to produce the products of the invention, other composi-
tions and procedures may also be employed to produce
products of the invention having substantially the same
degree of biological activity.
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