Note: Descriptions are shown in the official language in which they were submitted.
~L~L89~6~73
x l BA-8363
Tltle
PYRIDYL SULFONE HERBICIDES
Background of the Invention
Thls invention relates to pyridyl sulfones
which are useful as agricultural chemicals.
French Patent ~o. l,468,747 discloses the
following para-substituted phenylsulfonamides, use-
ful as antidiabetic agents:
N
R~S02-NH-C-NH ~
wherein R = H, halogen, CF3 or alkyl.
Logemann et al. Chem. Abstr., 53, 18052g (1959),
disclose a number oE sulEonamicles, inclucling uracil
clerivatives ancl those h~vin~ the E~rmula:
113C ~ ~ 80~N1ICNIlR
N =~
wherein R is butyl, ~henyl or ~ ~ /~
N
Rl
and Rl is hydrogen or methyl. When tested Eor hypo-
glycemic eEEec-t in rats (oral doses oE 25 mg/lOO ~,
the compounds in which R is butyl ancl phe1ly.l wer~
most pot~nt.
73
x 2
~ojciechowski, Acta Polon. Pharm. 19,
p. 121~5 (1962) [Chem. Abstr., 59 1633e] describes
the synthesis of N-[(2,6-dimethoxypyrimidin-4-yl)-
aminocarbonyl]-4-methylbenzenesulfonamide:
OC~I3
3 ~ SO2N~I-C-~IH ~\ ~N
OC~3
Based upon similarity to a known compound, the author
predicted hypoglycemic activity for the foreyoing
compound.
15Netherlands Patent 121,7S8, published Septem-
ber 15, 1966, t~ach~s th~ p.r~p~xak:Lo~ o~e compollnds
of ~x~ la (i), In~l kh~ s~ ~3 ~ r ~ v~
herbic.icl~s,
~1
r ~ N ~
R4 ~ ~2 N ~ (i)
R3 NHR
25 wherein
R1 and R2 may independently be alkyl oE 1-4
carbon atom5; and
R3 and R~ may independently be h~ydxo~en,
chlorine or alkyl o~ 1-4 carbon atoms.
30Compounds o~ ~ormula (ii), and their use as
antidiabetic agents, are reported in J. Drug. Res.
6~ 123 (1974).
~ S (ii)
~S "
SO2NHCNHR
wherein R is pyridyl.
In copendin~ Canadian patent application 328 446
to Grantham & Levitt, filed 1979 May 24, herbicidal
compounds such as N-heterocyclic-N'(arylsulfonyl)
carbamimidothioates (or compounds wherein a thienyl
radical is substituted for the aryl radical), such
as methyl ~ (2-chlorophenylsulfonyl)-N-(4-methoxy-
6-methylpyrirlidin-2-yl)carbamimidothioate are
taught.
United States Patent 3,689,549 to
R. P. Williams discloses "heterocyclic sul-
fonamides whexein the heteroatoms are inert can be
used, e.g., compounds having the furan, thiophene
or pyridine nucleus," in the production of sulfonyl
isocyanates from sulfonamides in a sulfolane sol~
vent.
B. G. ~oggiano, V. Petro~J, O. Stephe~son and
. M. ~ild, in ~
13, 567-574 (196.l) ~isclose ~h~ ~ollowincJ com};~ulld.s
which w~r~ ~estecl ~or hypog.~c~mic ~ctiv.i~
~
~ ~ - So2NHcNH(c~l2)3c~3
1~
where -SO2NHCNH(CH2)3CH3 is in the 2 or 3 position.
J. Delarge in Acta Pol. Pharm. 34, 245-249
(1977) discloses ?~-alkylcarbamo~lpyridinesulfonarmides,
as d~scribe~ in the structure below, as mild anti.-
in~lammatory agents and strong diuretics.
~ O
R - t - SO~NHCNHR'
~ N
7~
x 4
R = 3-, 4-, 5-, 6-Me, 2-, 4-, 6-Cl, 3-Br,
4-Et2N, 4-Me2CHNH, 4-(3-ClC6H4)NH,
4-(3-CF3C6H4)NH
R' = Et, Pr, Me2CH, Bu
O
SO2NHCNHR in 2-, 3- and 4-position.
German Patent 2,516,025 (November 6, 1975) to
J. E. Delarge, C. L. Lapiere and A. H. Georges dis-
closes the following compounds as inflammation in-
hibitors and diuretics.
R4
R2
2NHR '
N R4 = XR
(n)
R ~ C6~l~R3 ~3 ~ Cl, CF3, ~, M~O, El, ~r,
F, NO2, Ek, N~I~), Ek, .i~o-Pr, ~-m~khy.l
furyl, C6H3~12-~ C6~I3(Cr3)
R' = alkylcarbamoyl, cyclohexylcarbamoy:L, aryl-
carbamoyl, CS~IHCH2CH=CH2, CONHC6H4Cl-p,
alkylthiocarbamoyl, ~I, COEt;
R = H, Me;
X = NH, NMe, O, S, NEt; and
n = 0, L.
United States Patent 3,346,590 (October 10,
1967) (to K. Dickere and E. K~hle) disclosos th~
following pyridinesul~onyl isothiocyanates as nov~l
compounds.
SO 2NCS
3, S02NCS
73
x 5
Chem. Abstr. 83 16395lp (1975) reports pre-
paration of several 3-substituted 2-alkylsulfonyl-
pyridines:
N SO2R ~ R ~ 522NH2
I II III
wherein
R = CH3 or C2H5;
R = SH, SR, SO2R or Cl; and
R = Cl, SH or SO2C2H5.
15 Compound II with Rl = SO~C2H5 is reported to give 96.9Q
inhibition of gluconeogenesis in rat renal cortex
tissu~.
The pres~nce oE undcsi~d Ve~J~ta~iOrl ~ lS~
9ub~an~1 cl~m~ r~p~ a.Ll.~ J~
cultural produc~ h~t ~a~ fy man's b~sic ~o~cl ~n~;l
fiber needs, such as cotton, rice, corn, whe~t, so~-
bean and the like. The current population explosion
and concomitant world food and fiber shortage clemand
improvements in the efficiency o~ producing these
crops. Preventing or minimizing the loss of a por-
tion of such valuable crops by killiny or inhibitin~
the growth o undesired vegetation is one way o .im-
proving this efficiency.
A wide variety oE materials useE-ul ~or kill.in~
or inhibiting (controlling) the growth oE uncleslr~
vegetation is available; such materials are commonly
referred to as herbicides. The need e.~ists, however,
for still more effective herbicides that destroy or
control weeds without causing significant damage to
useful crops.
g~73
x 6
_mmary of the Invention
According to thi 5 invention, there are pro-
vided novel compounds of Formula (I) and their
agriculturally suitable salts, suitable agricultural
compositions containing them and methods of using
them as pre-emergence and post-emergence herbicides
and as plant growth regulants:
W
/ ~ S02I~H-C-NH-A
(I)
N
wherein
Cl C6 ~l]cyl, C3-C6 alk~n~l, C2-C~
~co~ ]c~ 5-C~ c~c~ c!~
R OCEI2CII~OCII~, R OCH~C'II~O~}[~CII~,
R
~C~I2)n ~ ~ CF3, CF3CII2 ~ ~IC~IC~2;
R
Rl is meth~l or ethyl;
R2 and R3 are independently H, Cl, OCH3, F,
CH3, Br, N02 o:r CF3;
n is 0, 1 or 2;
G is F, Cl, Br or CF3;
L is F, Cl or H;
Z is H, F, Cl, Br, CH3, CH30 or CH3S;
W .is O or S;
X ~'
N ~ N ~
~NO~E or ~ o~ ~ ;
X is CH3 or CH30;
73
x 7
Y is CH3, CH3CH2, CH30, CH3CH20,
3CH20, CrI30(CH2) m' CH30CH2CH20,
R402C-CHo, (CH3)2N or CH3NCH2CN;
E is C~I, N~ C-CH3, C-CH2CH3 or C-CH2CH2Cl;
5 ' 3 3 2;
R is H or CH3;
m is 1 or 2;
X~ is H~ CH3, CH30 or Cl; and
Y' is 0 or CH2;
and their a~riculturally suitable salts.
Preferred in order of increasing activity
and/or lower cost and/or ease of synthesis are:
1) Compounds of Formula (I)
wherein ~he substituent RS02 is
~t the 2--positio~ oE -th~ p~:rkli.n~
ring;
2) Compoullcls o:~ ~r~ .rr~cl tl) wh~.r~.n
0;
3) Compouncls of Pre:Eerr~cl (2) wherein
Z is ~1;
4) Compounds of Preferred (3) wherein
R is Cl-C4 alkyl;
5) Compounds of Pre:Eerred (4) wherein
Y is CH~ CH30 or CH3CH20;
6) Compounds of Preferred (5) wllerein
E is CH or N.
X
Specifically Preferred for highest activity
ancl/or lowest cost and/or greatest ease of synthesis
are:
M-[(4,6-Dimethylpyrimidin-2-yl)aminocarbonyl]-2-
(methylsulfonyl)-3-pyridinesul~onamide;
N-[(4-Methoxy-6-methylpyrimidln-2-yl)aminocarbonyl]-
2-(methylsulfonyl)-3-pyridinesulfonamide;
N-[(4,6-Dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-
2-(methylsulfonyl)-3-pyridinesulfonamide;
N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-
(methylsulfonyl)-3-pyridinesulfonamide;
N-[(4,6-Dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]-
2-(methylsulfonyl)-3-pyriclinesulfonamide;
~I-[(4-Methoxy-6-methyl-1,3,5-triazin-2-y].)amino-
carbonyl]-2-(methylsulfonyl)-3-pyridinesulfon-
amide;
~i-[(6,7-Dlhyclro-4-mctllyl-5EI-cycJ:lope:nkarJy~.lm:ldin-2~
yl)~minoca.r~onyl]~2~(m~tlly~ J..~onyl) ~py.~.lelln~
sul~onam~cle;
N-~fi,7-Dihyclro-~-m0thoxy-5H cyclopentapyr:Lm.ic~
2-yl)aminocarbonyl]-2-(metllylsulfonyl)-3-pyri-
dinesulfonamide;
N-[(5,6-Di}lydro-4-methyl~uro[2,3-D]pyrimidin-2-yl)-
aminocarbonyl]-2-(methylsulfonyl)-3-pyriclinesul-
fonamide; and
N-~(5,6-Dihydro-4-methoxyfuro[2,3-D]pyrimidin-2-yl)-
aminocarbonyl]-2-(methylsulfonyl)-3-pyriclinesul-
~onamide.
X g
Detailed Description
Synthesis
Pyridinesulfonyl isocyanates IV can be made
by the method of Ulrich et al. [J. Org. Chem. 34, 3200
(1969)] from a sui-tably substitutecl pyridinesulfon-
amide II:
,~_~ " S02N 2 ~ S2NS
1.RS02~)J SOC12~ RS2 ~J
/r N z
II III
COC12, pyridine ~ S2NC
~ > RSO
(solvent) y
/ N
IV
The sul~onam.id~ ls bo~ d uncl~r r~.lux w.l.th
excess o~ thiony.l cll.lorid~, wh.lah ~unc~:Lon~ a~ a
reactant and solvent. The r~action is continuecl unt:ll
the sulfonamicle protons are undetectable in the proton
resonance spectrum. An overnight reaction period
(about 16 hours) is frequently sufficient, though
several days (e.g. 5) may be required in some cases
to convert completely the sulfonamicle II to the
thionylamide III. The thionyl chloride is evaporat~d
and the residue treated with an inert solvent (e.cJ.,
xylene, toluene, benzen~, etc.) at least olle eclu.~va-
lent of phos~ene, ancl a cataly-tic amount o~ pyri-
dine. The mixture is heated to abou-t G0-1~10, wikh
80-100 preferred. Conversic)n to the isocyanate
is substantially complete within about 1/4 to 3
hours. The mixture containing the isocyanate can be
used directly for the next reaction step [formation
x 10
of compound (I), with W = O] or isolated in purified
form by filtration and/or evaporation of solvent.
Pyridinesulfonyl lsocyanates IV can also be
made as shown in reaction 2:
SO~NH
2. RSO2 ~ Crl3(CH2)3NC ~ S2NC
z N COC12, cat. z ~ N
II IV
The sulfonamide II, an alkyl isocyanate (e.g.
butyl isocyanate~ and a catalytic amount of 1,~-
diaza[2.2.2]bicyclooctane (DABCO) in xylene or other
solvent o~ sufficiently high boiliny point (e.y. ~135)
are mixed and heated to about 135, phosgene is added
until an excess is present (indicated by a drop in
boilin~ point). The m.txture .i~ ~uxth~r heat~cl ~ncl
e~coss phoscJ@n~ driVell 0~ k~r ~kh~ mLx~uxe .l~
cool~d ancl El.lt~rccl from i~so:Lubl~ m~k~r~ h~
~olvent, alkyl ~socyana~ ancl exc~ phosJ@rl0 ar~
evaporated, leavincJ the sulEonyl isocyanat.e IV. I~
desired, the alkyl isocyanate/sulfonamide adduct can
be made and isolated beEore reaction with the
phosgene; in that case the sulEonamide II, alkyl
isocyanate and anhydrous base (e.g. K2CO3) in an
unreactive solvent (e.g., acetone, butanone or
acetonitxile) are mixed and boiled under reElux ~Eor
]./2 to 4 hours, ~ollow~d by d.ilu~ion o~ -the r~act.ion
mi~ture with watex and adjustment o~ pH to abou~ 3
with acid (e.g., ~ICl, H~SO~, etc.), ;Eollowecl b~
tration to provide the adduct, which can be reacted
with phosgene as described above.
X 11
Pyridinesulfonyl isothlocyanates ~I can be
made by the method of Hartke [Chem. Abstr. 64,
15783e (1966~] or U.S. Patent 3,346,590 (see above):
2 2 ~ SK
3. P~SO2 ~ CS2, KOH ~ SO2N=C
N (DMF) 2
Z Z
II V
R502 --~ 502NCS
VI
The suleonami¢l~ in ~r~E~ is ~a~tl w.ilh an
equival~nk o~ carbon cl~ .id~ and 'tWQ ~C~ .V~ ,'J
of powdered potass.ium hyclroxicle at about 35~; okher
bases, includlng non-nucleophilic bases e-g.
sodium hydride, can be used instead of KOII. The
mixture is stirred (about 1-8 hours) until solution
is substantially complete, then diluted with an apro-
tic solvent (e.g., ethyl acetate) to precipitate the
~5 intermediate potassium salt V. The latter is separated
by filtration of the xeaction mixture, suspended i~ an
inert solven~ (e.g., toluene or xylene) alld t~reat~e~
with two moles of phos~ene ~or thionyl chlo~idc~e-t~.) at
about 0. The mixture is allowed to warm to ambient
temperature, filtered and the sulfonyl isothiocyanate
used as-is for formation of compound (I), with W = S,
or isolated by evaporation of the solvent. The sul-
fonyl isothiocyan2tes may dimerlze or trimerize in
some cases, but the dimers and trimers still produce
the compound (I).
~lr73~
x 12
The sulfonyl isocyanate IV or isothiocyanate
VI reacts with the aminoheterocyclic compound to
provide the pyridyl sulfone (I):
~ SO2NCW
4. RSO2 ~ J + H2N~A - -
VII
1 0 , W
~ S02NHCI~H-A
RS2 ~)J
(I)
This reaction i5 best clone in an iner~ or-
ganic ~olvent (~.q. ~tollitr:i.le, ~kr~hy;lr~Fl1r~rl,
methylene chloricle, e~a.). Th~ r~actan~ m~y b~
~d~d in ~y ~.~cl~ h~ r@~ n ~ cJ~
thermic. Conveniell~ly, the startincJ r~ac~.ion t~mper-
ature is ambient, but it can be varied from about
0 to 100 if desired. The product can be isolated
by filtraticn if it precipitates from the reaction
mixture; otherwise the solvent can be evaporated and
the residual product obtained thereby, with optional
purification through trituration with an organic sol-
vent (e.~. diethyl ether, l-chlorobutane, etc.) in
which i~ is only sparingly solubl~, or by rec:ry-
s tallizatio
~37~
x 13
An alternative method for preparation of
compounds (I), with W = S, is to react sulfonamide
II with a heterocyclic isothiocyanate:
SO2NEI2
5. RSO2 ~ ~ ',CN-A -~
N
II
1 0 S
~-~ S02MIICNH-A
RS2 ~J
N
(~), w.~kh
~ 'h~ .r~y~ h;lo~y~
procedu.re can b~ macle, Eo~ ~x~mp:L~, by ~h~ m~ thocl
of Japan Patent Application Pub: ~okai 51-143686,
June 5, 1976, or that of W. Abraham and G. ~arnikow
Tetrahedron 29, 691 (1973). ~eaction 5 is best
carried out in an inert, polar solvent (e.g., acetone
or butanone) at 20 to 50, in the presence o:E a
basic catalyst (e.g., K2CO3 or Na2CO3), durinq about
1 to 10 hours. The alkali metal salt o:E (I), with
W = S, is Eiltered oEf, suspenclecl in water, ancl th~
pH adjusted down to 1-3 with acicl (e.g., ~l~l or H2SO~)
to form pyridyl sul:Eone (I), with W - S, x~cove.recl ~y
filtration.
~8~YV7,3
x 14
The starting pyridinesulfonamides II can be
made by one or more of the illustrative methods
shown below:
6. ~ 5l2NH2 EtSH ~ ~ SC2NH2
VIII IX
[o] ~ S02NH2
S2E t
X (compound II with
15 [Re~: Chem. Abstr. 83, R - F,k
163951p (1975)] Z, ~ :M)
Thus, a mexcapt~n xe~c~s w.i~th ~h~ chlo.xo~y.~icl.l-ne
compou~d in the p~^esellc~ O~e a b~s~ to .~o:~m ~h~
sul~ide IX, which is then oxicli~ecl to the sulone X.
/ ' N2 + - /-- N02
7 ~ + r~aO2SCH3 ~ f~
. ~ N ~ Cl (DMF) ~ N ~ ~ S2CH3
XI XII
1 HONO HCl
~5~ ~NH2 S , CuCl
N S2CH3
XIII
~ S2Cl ~H3 ~ S2NH2
N S2CH3 (THF) N S2C~I3
XIV XV
~: 15
In reactior. 7, the chloronitropyridine reacts
with sodium methanesulfinate in the prese~ce of a
solvent Ipreferably a polar, aprotic solvent e.g.
N,IY-dimethylformamide (DMF), dimethyl sulfo~ice
5 (D.~O~, N,N-dimethylacetamide (D~C), tetramethyl-
e~esu:lfone (sulfolane), etc.] at a temperature from
about ambient up to the boiling point of the solvent,
to provide the sulfone XII.
Other halonitrop~ridines can be substituted
for XI and other sulfinic acid salts for sodium me-
thanesulfinate, aepending on the particular sulfone
desired. Reduction of compound XII to the amino
compound XIII can be accomplished by conventional
route~s, e.g. with iron and aqueous acetic acid,
or catalytic hydrogenation Diazotization of the
amine XIII at about -10 to 20 ~preferably O to 10)
in the presence of HCl and subseouent treat~ent ~ith
S07 and a copper specles ~such as cuprQus or CllprlC
chlo~ide), at about ~10 to 50 ~pr~exably abou~ O to
30) produc~s the sulfonyl chlorid@ ~IV. RQacting
the chloride XIV wi~h anhydrous a~monia in a solvent
~e.g. tetrahydrofuran ~T~), methylene chloride, butyl
chloride, toluene, die~hyl ether, etc.] or ~th aaueous
ammonia produces the sulfonamide XV; the amination can
~5 be conveniently accomplished at about -10 to 50, with
0 to 30 preferred.
07~
x 16
~lhen R is haloethyl or halop,ropyl', the com-
pounds II can be prepared as illustrated in reaction 8
for the tetrafluoroethyl compound XVIII:
NH2 (base catalyst)
8. ~ + CF2= CF2 DMF
N SH
XVI
NH2 steps as in reaction
/\~ . .. .. ,
1 sequences 6 and 7
. `N SCF2CHF2
XVII
~ SO~N~
~l
N ~c~C~
XVIII (compouncl II with R~ ~ CF~C~l;F2
z = H.)
Compound XVI is described in Polish J. Chem.
52, 2041 (1973). Reaction of aminopyridinethiols
with the haloalkenes occurs at 0 to 100 in an inert
solvent, e.~. D~lF, in the presence of a basic
catalyst such as diisopropylamine or potassium
hydroxide. The additional steps are carried out as
described for reaction sequences 6 and 7.
7~
x 17
When R is trifluoromethyl, the compound II
can be made as shown:
- ~ SCH3 ~ N
N SCH3
XIX XX
o
Cl;~ ~;XN~ F
hv N SCC13
XXI
O
2 0 ~N J~5C F ~ (~ 5 2CF3
XXII XXIII
N H ~ NH~ steps as in part
~ O
~ ~ ~ of reaction
N S2CF3 sequence 7
XXIV
~ $02NH2
~l
S02CF3
XXV (compound II with R = CF3,
æ = H)
~Re~. for similar procedure through compound XXIV:
Chem. Abstr. 70, 96324c (1969)].
3g~7i3
x 18
Thus, the methylthio compound XIXis phtha-
loylated by phthalic anhydride in acetic acid to
compound XX, which is chlorina~ed photolytically to
compound XXI. Halogen exchange is accomplished with
HF or SbF3 to prepare compound XXII, which is oxi-
dized to the sulfone XXIII, from which the phthaloyl
group is removed by hydrazine to provide the amine
XXIV. The amino compound is converted to the sul-
fonamide as described in reaction sequence 7~ Al-
ternatively, the c~mpound XXV with R as trifluoro-
methyl can be made as shown:
H2 ~ u Cl KSH
XIX XXVI
o
2Q ~ ~ CF~X,h~
N SH
XXVII
O
~ as in reaction
25 ~ N ~ sequence 9
N SC~3
XXII
~N X 02NH~
02CF3
XXV
19
The chloroaminopyridine is phthaloylated
as clescribed for compound XIX. The thiol XXVII is
made as mentioned for compound XVI, and the tri-
fluoromethylation is done as described in
Chem. Abstr. _, 134226h, with trifluoroiodomethane.
The synthesis of sulfur compounds of pyridine
has been reviewed in "The Chemistry of Heterocyclic
Compounds", a series published by Interscience
Publ., N.Y. and London. Pyridinesulfonamides are
described by H. L. Tale in "Pyridine and Its Deri-
vatives" Supplement, Part 4 (1975).
The compounds of this invention can be made
by the teachings discussed or illustrated in the
examples and tables which follow, wherein all
parts and percentage~ are by w~icJhk ~nd ~@mpera~ures
are in cle rees c~nki~rade
~89~73
x 20
Example l
CH3
Preparation of ~ S02NHCONH -~ ~
SO2C~3 c~3
~X + NaS02CH3 ~ I'ôX N2
N Cl N S2CH3
XI XII
A mixture of 22.1 g (0.139 mo:Le) of 2-chloxo-
3-nitropyridine, 14.5 g (0.142 mole) of sodium methane-
sulfinate and 150 ml of D~ was boiled under reflux for
l hour. The Dl~` was evaporated in vacuum and the
residue extrac~ed wikh ekh~l ace~ ho ethyl
aceta~e ex~ract was washed ~ h wat~, dilute b~in~3
and sa~ur~ed brin~, clri~d ~M~O~ ancl c~aporc~t~ n
vacuum to an oil. The oil wa~ crys~alliz~d ~rom bu~yl
chloride and the solid twice recrystallized from ace-
tone/hexane to provide 9.1 g of the sulfone XII as a
tan solid, m.p. 104-107.
b. ~ NO2 ~
N SO2CII3 SO~CH3
XII XIII
A solution of 9.68 g (0.0~79 mole) o~ the sul-
fone XII in 50 ml of acetic acid was treated with 12.5
ml of water, then, portionwise with 11.5 g
of powdered iron. The temperature was kept at <95
during the exothermic reaction by periodic
cooling. After an additional 10 minutes at about
83 the mixture was filtered, the filtrate diluted
~1!3~t73
x 21
with water and the pH raised to about 6 by gradual
addition of 50~ NaOH, with cooling to ~25; the
solution was then evaporated to dryness in vacuum.
The residue was treated with ethyl acetate and
sodium bicar~onate, the ethyl acetate solution dried
(MgSO4), filtered, and evaporated to 7.41 g of a
syrup, which was the amine XIII. Mass spectral
analysis of the syrup showed the expected mole-
cular ion, m/e 172, for amine XIII.
~NH2 ~S2
S2CH3 N S2CH3
XIII XIV
A solution o~ 6~73 g ~0.0391 mol~) o~ th~ ~mino-
pyridyl sul~one XIX~ in 9 ml of ac~tlc flCid wa~ a~d
to 29 ml of cold conc~ ~C1 ~t 0 to 10. ~`h~ ~olu~lon
was treated, portionwise, at 0 to 5, with a solution
of 3.83 g of sodium nitrite in 10.2 ml of water, with
development of an orange color. After an additional
1~ minutes at this temperature, the diazonium mixture
was added, in portions, to a stirred mlxture of 1.1 q of cuprcus
chloride, 8 ml ~liquid) of sulfur dioxide and 42 ml
of acetic acid at 5 to 15 gas evolution occurred
rapidly throughout the addition. After an additional
15 minutes, ~he mixture wa~ warmed to 2S, and the
resulting mixture poured into excess ice water~ Pre-
cipitated white solid was filtered off, washed with
water, and dried, providing 5.26 g of the sulfonyl
chloride XIV as a white solid, m.p. 162-163~dec.).
~ 9~'73
x 22
d. ~ S2Cl NH3 ~ S2NH2
N S2C~3 N S2CH3
XIV XV
The sulfonyl chloride XIV obtainecl in Part c
was dissolved in THF, eooled in an ice bath and
gassed with ammonia, with a resulting exothermic
reaetion along with the preeipitation of a white
solid. The mixture was evaporated in vacuum
to a white solid, which was washed with water to
remove ammonium ehloride, leaviny the sulfonamide XV
as a white solid, m.p. 195-196.5. Mass speetral
analysis of the solid showed a moleeular .ion
m/e 237 ~m ~ 1).
e. ~ ~O~N~{~
N S2C~13 N 50~C~-13
XV XXVIII
~ O2NCO ~ O2N}ICONH-< ~
XXIX XXX
one gram (0.00~23 mole) of the s~l:L~onam.ide ~V
was suspended in 100 ml of thionyl chloride. The mix-
ture was boiled under reflux for about 3 days, disso-
lution of the sulfonamide occurring in 10-15 minu-tes.
The solution was evaporated to a elear, brown
oil (XXVIII). An exeess of solution of phos~ene in
73
23
toluene (13.8% phosgene solution) was added along
with 3-4 drops of pyridine. The mixture was heated
at 85 under phosgene reflux for 2 hours, cooled,
and filtered. The filtrate was evaporated to a
solid (XXIX), which showed a strong isocyanate
absorption peak in the infrared spectrum (ca. 2250
cm 1, Nujol* mineral oil mull).
The solid isocyanate was dissolved in a little
acetonitrile and treated with 0.5 g of 2-amino-4,6
dimethylpyrimidine, a reaction quickly occurring
with precipitation of white solid. After a few
minutes the mixture was filtered and the white solid
washed with acetonitrile and butyl chlor:Lde, leavincJ
0.71 g of the pyridyl sulfone XXX as a wh:ite soli.d,
m.p. 234 (dec.). Mass spectral analysis
showed m/e 236, ~ 02N1l2 ~ ~nd m/e l~
N ~C113
C~13 ~.
OCN ~ 0~
CH3
~nal. Calcd. Eor XXX, Cl3H15N505S2(M.W. 385.42):
C, 40.5; H, 3.9; N, 18.2.
Anal. Found:
C, ~0.8; H, 4.0; N, 18.5.
*denotes trade mar]i.
~,
~'~..~,,'
~L93~73
x 2~
Table I
~ ?~ ~ S02NHC-NHA
RSO2~ (I)
RSO2 _ W A_
CH3
2-CH3SO2 H O~N~
OCM3
2-CE~3 S02 H O~No~
OCH3
CEI3
CM3S2 EI
~C~-I3
202-CI13SO2 EI O_( O~
OC~ 3
2-CH3S02 H O~ O~
NV
2 5 CH3
N~
2-CH3SO2 H O~ o~h
CEI3
N _~C H 3
302-CM3SO2 H ON t
OCH3
(CH3
2-CH3SO2 H O N~
OCH 3
CEI
2-CH3SO2 H O~N~
N ~N - CH3
CH2CN
x 25
Tabl e I ( continued )
RSO2 Z W A
N~
2-CH3S02 H O ~NO~
OCH
2-CH3SO2 H O N~
2 - CH 3 S 2 H O N ~C~ 3
CI~3
2-CH3SO2 H O ~NNo~
l 5 OC2I-Is
c~; 3
2-CH3$0~ H O
N ~ Ci13
2~ CH3 S 2 11 G)
cr''I20CH3
c~3
2-CH3SO2 H O N~
CH2CH2C~I3
N CH3
2-CH3S02 H O N(~
OCH2CH20CH3
3 0 N ~13
2-CH3S02 H ~NO~
CH2CQ2H
c~3
2-CH3SO2 H O ~ ~
2 2 3
x 26
Tabl e I ( c ont i nued )
F<S02 _ W A
C~l
N~ 3
2-CH3S02 H O ~0~
OCH2C02C2H5
2-CII3S02 H O ~NO~
O ( 3 ) 2 3
2-CH3S02 H O ~N~)$H3
N(CH3) 2
_~ CH3
2-CH3S02 H O N~) ~ 3
~-C~I ~C~i
~ O~Ii3
2-CEI3502 M O ~ 1~
OCII ~ OC II
()~li 1
2-CH3S02 H 0 ~1
OC~i2C02
~OC '-I 3
2-CH3S02 H O -<NO~N
OCM2C02Ci-i3
OC~
2-CH3S02 H O N
~C~12C02C2~5
2-CH3S2 H O
OCH (CH3 ) C02C~I3
OC~-'
2-CH3S02 H O N (CH3) 2
D73
x 27
Table I (continued)
RSO2 z ~ A
N_~OCH3
2-CH3SO2 H O ~ O~
C2H5
2-CH3S02 ~1 o <~o$ 3
OC2Hs
,OCH
2~CH3S2 H O ~ O~
CH 2CF 3
_~OCII 3
2-CIi3SO2 H O N~
1 5 C~120CH3
OC~Il
'`-Cll SO M Q ~T
CEI2CM2Qe~II3
1 3
2-CH3SO2 H O ~ ~Cll3
N-C~i 2CI~
CM
2-CH3S02 H O ~ o~CH3
CH3
C ~I 3
2-CII3SO2 H O ~IO~CM2CH3
~13
3 0 CH3
2-CH3S02 H O ~ o~ C~12CH2Cl
CM3
N~
2-CH3SO2 H O ~NO~
73
x 2~
Table I (continued)
RSO2 z W A
C~I 3
2 -CH 3 S 2 H O -~ O~
OCEi
2-CH3S02 H O ~
2 - CH 3 S 2 H O ~NNO ~,
N-~
2-CH3S02 H ~NO~
O
N-~CIl3
3 ~) 2 H ~NO~
OCII~
2-CII3 SO2 ~I O N
Cl
2 -CH3 S02 H O N$~
o
OCH 3
2-CH3S02 H O `(~
C 2Il 5
OCH
3 0 ~ 3
2-CH3SO2 H O N~
OC 2~s
2 - CE~ 3 S 2 H O ~OCH 3
73
x 29
Table I (continued)
2 _ W A_
~ OCH3
2-CH3SO2 H O ~NO~
CH20CH3
2-CH3SO2 H O ~Jo~)
CH2('H20CH3
OCI-I
2-CH3SO2 H O ~ O~
OCH2CH20CH3
OCH
2-CH3SO2 H ~No~
1 5 OCH~CO~M
OC Ll
2 CH3S2 El (~
I2~ }13
2-CH SO H O ~)
3 2 N
OCH2C02C2~[5
OCH3
2-CH3SO2 H O -( O~
N ~:~CH (CE-I3 ) C2CE~3
2-CH3$2 H 0 ~ $CH3
N-C~ CN
3 0 N ~CM 3
2-CH SO H O ~ O ,N
3 2 C2H5
~L~o~ CH3
2-CH3SO2 H O - N
x 30
Table I (continued)
RSO
2 Z W A
~ CH3
2-CH SO H o ~ O~d
3 2 N~
2 3
~ ~c~3
2 - CH 3 SO 2 H ~(N~C'
H20CEI3
1 0 ~CH3
2-CH3SO2 H O ~NO~
CH2CH20CH3
N _~CH3
2-CH3S2 }I ~!?y~
OCEI 2CH 2 OCH 3
N ~Cii3
2-CH3S02 El O ~N ~
C:li2C0 ~1I
2 0 2 -CI1 3S~)2 1~
CI12C02CH3
_~ CEi3
2-CH3SO2 H O ~NO~
OCH2CO2C2H5
N_~CEi 3
2-CH3S02 H o ~~ O~
OCEI ( H3 ) 2 3
3 0 _~CH3
2-CEI3SO2 H O N~
N(CEI3) 2
N CH3
3 2 ~NC~)
CH3
73
x 31
Tabl e I ( continued )
RS02 z W A
2-CH SO G-Br O ~( ~
3 2 CH3
2-CH3S02 6-F O~0~ H3
CH3
2-CH3S02 6-CH3 ~ ~CEI3
CII 3
N _~CH 3
2-CH SO 6-CEI30 ~ ~)
N CH3
2 - C EI 3 S 2 6 - C~3 ~(~
~CI.13
2 -CH 3 SO 2 H SN(~
CH3
_~ CEI 3
2-CH3S02 H S<NO-~)
OCH3
CH3
H 3 2 S ~
C~I3
3 0 _~CH3
2-CH3S02 H S
CEI3
2-CEI3S02 H Si~I ~
7q~
32
Table I (continued)
RSO2 Z W A
OC~
~ 3
2-CH SO H S ~ O
3 2 N~
OCH 3
2-CH3CH2SO2 H O CEl3
CH3
102-CH3 (CH2) 5SO2 H O N~
CH3
N _~CH 3
2-CII2=CHCH2SO2 H O ~r~cH
2~ CEI3 (CEI 2 ) 2CEI=CHCH2SO2 H ~CE3
202-CH30CH2S02 H -(rlb~,
2-C H OCE1 CH SO H O
252 5 2 2 2 N H3
( CII3
2-CH30CH2CH20CH2S02 H O -~~)
3 0 ~_~CEI3
2-C2H5OcH2c~I2OcH2so2 H O N~cH
CH3
2-CH3OCH2CH2oCH2CH2So2 ~N~)
CH3
x 33
Table I (continued)
RS02 z
N~ C~3
2-C2H5Oc~l2c~2Oc~2c~2so2 H ~H3
N ~CH3
4 C 3 2 H O ~NO~
CH3
104 C 3 2 H O N~
OCH3
~C~13
4 3 2 H O ~NO~
OCH3
I`l-~CH3
3 2 H O ~NO~
CH3
N ~OCH3
204-CH3sO2 H O ~NO~J
OCrI3
c~3
4-CH3sO2 H O N ~
OCH3
N~ 3
5-CH3sO2 H O ~NO~
CH3
OCH3
5-CE3sO2 H O ~
OCE3
CH3
N~
5 C 3 2 H O ~NO~
OCH3
- ~L~7~
x 34
Table I (continued)
2 Z W A
CH
N~, 3
5-CEI3S02 H 0 -~ 0~
T-I 3
3 2 H O ~lo 3
OC~i3
~Cl~I
~ 3
5-CE~3S02 H O N~
OCF~ 3
N ~CH 3
6-CE7 SO H O ~I~O~)
CH3
OCH3
6--CH3SO2 H O -(N~O~
OCH3
2 0 ~CIi3
6-CEI3SO2 H O ~NO~
CH3
CH3
6 - CH 3 S 2 H O C
H3
N CH3
6-CEi3So2 H ~NO~
OCH 3
OC~ 3
6-CH3SO2 H O ~ O~
c~3
OCH3
2-CH SO2 H O ~ ~)
3 N~
N (CH3) 2
~8~q3
x 35
Tabl e I ( continued )
RS0
2 Z W A
i
2- Q H 0 ~NO~H3
S2 N I13
CH3
2- O~ H 0 ~0~
S02 cHH3
2- ~}S2 H 0 CH3
N _~:H 3
2- Cl~S0,, H (N0~
CII3
2 0 M _<CH 3
2- C'H 30~S0 H 0
CH3
2- F~so2 H 0 ~p
2- CEI 3~}S02 H o ~NN~)cH3
CH3
2- Br ~ S02 H N~CH
2"~ CI~3
2- ~} S02 H 0 ~N~I3
73
x 36
Tabl e I ( cont inued ?
RSO~
Z 1~ A
5 CF3
~ C~
2- <~ S02 H O~No~ 3
N--(CII 3
Cl CH
2- Cl--~ S02 H O~NIo~ 3
- CH3
2- ~ 2 2 H O ~CH3
C~I3
2- Cl~CH -SO H ~N~O~33
2- <~ 2 2 2 H O~ 0~)
CH3
2- Cl~CH2CEI2-s02 ` H O ~ 0~
N CEI3
2 - CF 3 S 2 H -(NO~')
CH3
2-~CF2CF2S2 H O ~CH3
CI-1 3
2-HCFClCF2so2 H O~NO~)
C~I3
7~
x 37
Tabl e I ( continued )
RS2 Z W
N ~CH3
2-HCFBrCF2SO2 H O ~ O>
~:II 3
N CH3
2--CF3E;CFCF2S02 H O ~NO~
CH3
CH3
2 2 2 H O ~O ~
CH3
N _<CH 3
2-H2CFCF2So2 H O ~~)
CH3
2 0 M-~C~I 3
2-CF3CH,~S02 H O ~ O~
CH3
~ ~89~3
x 3g
Table II
~ S02Cl
RS 2 ~)~
,7
RS02 Z
1~ _
2-CH3S02 H
2-C2H5S02 H
2-CH3~CH2)SS02 H
2-CH2=CHCH2So2 Ii
2-CH3(CH2)2CH=CHCH2S2 H
2-CH30CH2So2 H
2-C2H50CH2CH2So2 H
2-CH30CH2CH20CII2S02 H
2-C2H5CH2C~2CH2S2 H
2-CH30C~I2CH20C~12CH2S02 H
2-c2H5ocH2cH2ocH2c-I2so2 H
2-CIi3S02 6-Cl
2-CH3S02 6-Br
2-CH3S02 6-F
2-CH3S02 6-CH3
2-CH3S02 6-CH30
2-CH3S02 6-CH3S
3 2 H
5-CH3s2 H
6-CE3So2 H
2- ~ S2 H
35 2- S2 H
x 39
Table II (continued)
RS02
2- ~S02 H
2- Cl ~S02 E;
2- CH30 ~3So2 H
r~
2- F~sQ2 H
2~ CH3~ S02 H
15 2- 3r~}S02
SO2
2- 02N~ H
SO2
2- CF3 ~ H
25 Cl
2- Cl~} S02 H
2- <~} C~2S2 ~;
2- Cl-<~CH2S02 H
2- ~} CH2CH2S2 H
35 2- Cl~} C~I2CH2S2 H
g~73
Table I I ( continued )
SO2 z
-
52-CF3So2 H
2-HCF2CF2So2
2-HCFClCF2SO2 H
2-HCFBrCF2SO2 H
2-CF3HCFCF2So2 HH
2-HCC12CF;; S2 H
2-H2CFCF2So2 H
2-CF3CH2S02
~L8~
x 41
Table III
2 ~ S2~H2
RS02 z
2-CH3S02 H
2-C2H5502 H
2-CH3tCH2)5So2 H
2-CH2=CHCH2S02 H
3( 2)2 2 2 H
2-CH30CH2So2 H
2-C2H50CH2c~2s02 H
2-CH30CH2CH2oCH2So2 H
2-C2H50CH2C~20cH2s02 H
2-CH3CH2CH2C~12CH2S2 H
2-C2H50CH2C~20cH2c~2s02 H
2-CIl3S02 6-Cl
2-CH3S02 6-Br
2-CH3So2 6-F
2-CH3S02 6-CH3
3 2 6-CH30
2-CH3S02 6-CH3S
3 2 H
3 2 H
6-CH3So2 H
2- ~ S2 H
35 2- ~ S2 H
~7'3
x 42
Table III ~continued)
RS02 z
5 2- ~SO2 H
2- Cl-<~ S02 H
2- CH3O~so2 H
2- F~so2 H
2- CH3~ SO2 H
15 2- Br~SO2 H
SO2
2- O2N~ H
SO2
2- CF3 ~ H
25 C1
2- Cl~ SO2 H
2- <~ CE12S2 H
2- Cl~CH2SO2 EI
2- ~ CH2CH2SO2 H
35 2- Cl~ CH2CH2SO2 H
~. 8~7~3i
x ~3
Table III (continued)
RS02 Z
5 2-CF3So2 H
2 C 2 S O ~ H
2-HCFClCF2SO2 H
2-HCFBrCF 2 S2 H
2-CF3HCFCF2So2 H
2-HCC12CF2SO2 H
2-H2CFCF2So2 EI
2-CF3CH2So2 H
73
x 44
Table IV
,~ so2NCO
RS02 ~ ~
RS02 z
2-CH3So2 H
2-C2H5S02 H
2-CH3(CH2)5So2 H
2-CH2=CHCH2So2 H
3( 2)2 2 2 H
2-CH30CH2So2 H
2-C2H50CH2CH2So2 H
2-CH30CH2CH20CH2So2 H
2-C2H5CH2C~2CH2S2 H
30CH2CH20CE12CH2S02 H
2-C2H50CH2CH20cH2c~2s02 H
2-CIi3S02 6-Cl
2-C~3S02 6-Br
2-CH3S02 6-F
2-CH3S02 6-CH3
2-CH3S02 6-CH30
2-CH3S02 6-CH3S
3 2 H
3 2 H
6-CH3So2 H
2- ~ S02 H
35 2- ~ S02 . H
8~7;~
x 45
Table 1~' (continued)
_ __
~S2 Z
5 2- ~ S02 H
2- Cl-~ S02 ~i
2- CH30 ~S02 H
2- F~So2 H
2- CH3~ S02 H
1; 2- Br~S02 H
~ SO2
2- 02N~ H
SO2
2 - C F3~) H
Cl
2- C1~ S02 H
2- ~ C~2S02 ~i
2- Cl~CH2502 H
2- ~- CH2CH2S02 H
35 2- Cl~ CH2CH2S02 H
~7~
x '16
Table I~ (continued)
. .
RS02 Z
5 2-CF3So2 H
2-HCF2CF2So2 H
2-HCFClCF~SO2 H
2-HCFBrCF2SO2 H
2-CF3HCFCF2So2 H
2-HCC12CF2SO2 H
2-H2CFCF2So2 EI
2-CF3CH2So2
47
Table V
,~ S02~CS
2 ~ ~
RS02 z
2-CH3So2 H
2-C2H5So2 H
2-CH3(cH2)ss02 H
2-CH2=CHCH2So2 Ei
3(CH2)2CH CHCH2S02 H
2-CH30CH2So2 H
2-C2H50CH2CH2So2 H
CE130CEi2CH20CI12S02 H
2-C2H5CH2CH2CH2S2 H
3 CH2C120CE12CH2So2 H
2-c2H5ocH2cH2ocH2cI2so2 H
2-CIi3S02 6-Cl
2-CH3S02 6-Br
2-CH3S02 6-F
2-CH3So2 6-CH3
2-CEI3S02 6-CH30
2-CH3So2 6-CH3S
3 2 H
3 2
6-CH3So2 El
2- ~ S02 H
3; 2- ~ S02 H
~8~73
x 48
Table V (continued)
RS02 z
2- (~ S02 H
2- Cl-<~ S02 E;
2- CH3O ~}S02 H
2-- F{~so2 H
2- CH3~ SO2 H
15 2-- Br~} S2 EI
SO2
2- O2N ~ H
SO2
2- CF3-~ H
25 C1
2- C1~} S02 H
2- ~} CH2S02 H
2- Cl~CH2SO2 EI
2- ~CH2CH2SO2 H
35 2- C1~ CH2CH2SO2 H
~73
49
Table V (continued)
RS02 Z
5 2-CF3S2
2-HCF2CF2So2 H
2 -HCFClCF 2 S2 H
2-HCFBrCF2SO2 H
2-CF3HCFCF2So2 H
10 2-HCC12CF2SO2 H
2-H2CFCF2So2 H
2-CF3CH2SO2 H
73
x 50
Formulations
Useful formulations of the compounds of
Formula I can be prepared in conventional ways.
They include dusts, granules, pellets, suspensions,
emulsions, wettable powders, emulsifiable concen-
txates and the like. Many of them can be applied
directly. Spravable formulations can be extended
in suitable media and used at spray volumes of
from a few liters to several hundred liters per
hectare. The formulations, broadly, contain about
0.1% to 99gO by weight of active ingredient(s) and
at least one of a) about 0.1% to 20% surfactant(s)
and b) about 1% to 99.9% solid or liquid diluent(s).
More specifically, they will contain these ingredi-
ents in the approximate proportions set forth inTable VI.
Table VI
~eight Percent*
Active
Ingredient Diluent(s) Surfactant(s)
Wettable Powders 20-90 0-74 1-10
Oil Suspensions,
Solutions,
Emulsions (in-
cluding Emulsi-
25 fiable Concen-
trates) 3-50 40-95 0-15
Aqueous Suspensions 10-50 40-84 1-20
Dusts 1-25 70-99 0-5
Granules and
Pellets 0.1-95 5-99.9 0-15
*Active Ingredient plus at least one of a Surfactant
or a Diluent equals 100 weight percent.
~89~73
x 51
Lower or higher levels of active ingredient
can, of course, be present depending on the intended
use and the physical properties of the compound.
Iligher ratios of surfactant to active ingredient
are sometimes desirable r and are achieved by in-
corpora-tion into the formulation, or by tank mixing.
Some typical solid diluents are described in
Watkins, et al., "~landbook of Insecticide Dust
Diluents and Carrierst', 2nd Ed., Dorland Books,
Caldwell, ~ew Jerseyr but other solids, either
mined or manufactured, may be used. The more ab-
sorptive diluents are preferred for wettable powders
and the denser ones for dusts. Typical li~uid
diluents and solvents are described in Marsden r
"Solvents Guide", 2nd Ed., Interscience, New York,
1950. Solubility under 0.1% is preferred for sus-
pension concentrates, solution concentrates are
preferably stable against phase separation at 0C.
"McCutcheon's Detergents and Emulsifiers Annual",
MC Publishing Corp., Ridgewood, New Jersey, as well
as Sisely and Wood, "Encyclopedia of Surface Active
Agents", Chemical Publishing Co., Inc., New York,
1964, list surfactants and recommended uses. All
formulations can contain minor amounts of additives
2S to reduce foaming, caking, corrosion, microbiological
growth, etc.
The methods of making such compositions are
well known. Solutions are prepared by simply mixina
the ingredients. Fine solid compositions are made
by blending, and usually, grinding as in a hammer
or fluid energy mill. Suspensions are prepared by
wet milling (see, for example, Littler, U.S. Patent
3,060,084). Granules and pellets may be made by
spraying the active material on preformed granular
carriers or by agglomeration techniques. See
" ~L~73
x 52
J. E. Browning, "~gglomeraLion", Chemical Engineering,
December 4, 1967, pp. 147ff. and "Perry's Chemical
Engineer's Handbook", 4th Ed., ~IcGraw-Hill, New York,
1963, pp. 8-59ff.
For further information regarding the art of
formulation, see for example:
H. M. Loux, U.S. Patent 3,235,361, Col. 6,
line 16 through Col. 7, line 19 and Examples 10
through 41.
R. W. Luckenbaugh, U.S. Patent 3,309,192
Col. 5, line 43 through Col. 7, line 62 and ExamFles
8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164,
166, 167 and 169-182.
H. Gysin and E. Knusli, U.S. Patent 2,891,855,
Col. 3, line 66 through Col. 5., llne 17 and Examples
1-4.
G. C. Klingman, "Weed Control as a Science",
John Wiley & Sons, Inc., New York, 1961, pp. ~1-96.
J. D. Fryer and S. A. Evans, "Weed Control
Handbook", 5th Ed., Blackwell Scientific Publications,
Oxford, 1968, pp. 101-103.
Unless indicated otherwise, all parts are by
weight in the following examples.
Example 2
Wettable Powder
N-[(4,6-Dimethylpyrimidin-2-yl)aminocarbonyl]-2-
(methylsulfonyl)-3-pyridinesulfonamide 95%
dioctyl sodium sulfosuccinate 0.1%
sodium ligninsulfonate 1~
synthetic fine silica 3.9%
The ingredients are blended and ground in a
hammer-mill to produce particles almost all of which
are below 100 microns in si~e. That material is
sifted through a U.S.S. No. 50 screen and packaged.
7~
x 53
Example 3
Wettable Powder
N-[(4,6-Dimethylpyrimidin-2-yl)aminocarbonyl}-2-
~methylsulfonyl)-3-pyridinesulfonamide 40%
dioctyl sodium sulfosuccinate 1.5%
sodium ligninsulfonate 3~
low-viscosit~ methyl cellulose 1.5%
attapulgite 54%
The ingredients are thoroushly blended and
10 passed through an air mill to produce an average
particle size under 15 microns, reblended, and
sifted through a U.S.S. No. 50 sieve (O.3 mm
opening) before packaging.
Example 4
15 Granule
wettable powder of Example 3 25%
gypsum 64%
potassium sulfate 11%
The ingredients are blended in a rotating mixer,
20 and water is sprayed onto that blend so as to effect
granulation. ~7hen most of the granules have reached
1.0 to 0.42 mm (U.S.S. ~18 to 40 sieves) in size,
they are removed, dried, and screened. Oversize
material is crushed to produce additional materlal
in the desired range. The resulting granules contain
10% of the active ingredient.
Example 5
Wettable Powder
N-[(4,6-Dimethylpyrimidin-2-yl)aminocarbonyl]-2-
30 (methylsulfonyl)-3-pyridinesulfonamide 65%
dodecylphenol polyethylene glycol
ether 2%
sodium ligninsulfonate 4%
sodium silicoaluminate 6%
montmorillonite (calcined) 23%
54
The ingredients are thoroughly blended. The
liquid sur-factant is added by spraying on the solid
ingredients in a blender. After grinding in a
hammer-mill to produGe particles almost all of
which are below 100 microns in size, the material
is reblended, sifted through a U.S.S. ~50 sieve (0.3
mm opening) and packaged.
Example 6
Oil Suspension
N-[~4,6-Dimethylpyrimidin-2-yl)aminocarbonyll-2-
~methylsulfonyl)-3-pyridinesulfonamide 25%
polyoxyethylene sorbitol hexaoleate 5%
highly aliphatic hydrocarbon oil 70%
The ingredients are ground together in a
sand mill until the solid particles have been reduced
to under about 5 microns. The resulting suspension
may be applied directly, but preferably after being
extended further with oils or emulsified in water.
Example 7
Aqueous Suspension
N-[~4,6-Dimethylpyrimidin-2-yl)aminocarbonyl]-2-
~methylsulfonyl)-3-pyridinesulfonamide 25%
hydrated attapulgite 3
crude calcium ligninsulfonate 10%
sodium dihydrogen phosphate 0.5%
water 61.5%
~ The ingredients are ground together in a ball
or roller mill until the solid particles have been
reduced to sizes under 10 microns, and then packaged.
073
x 55
Example 8
Extruded Pellet
N-[(4,6-Dimethylpyrimidin-2-yl~aminocarbonyl]-2-
(methylsulfonyl)-3-pyridinesulfonamide 25%
anhydrous sodium sulfate 10%
crude calcium ligninsulfonate 5%
sodium alkylnaphthalenesulfonate 1%
calcium/magnesium bentonite 59%
The ingredients are blended, hammer milled and
then moistened with about 12% water. The mixture is
extruded in the form of cylinders about 3 mm in dia-
meter which are cut to produce pellets about 3 mm
lon~. The pellets may be used directly, after dry-
ing, or dried pellets may be crushed to pass a U.S.S.
No. 20 sieve (0.84 mm openings). The granules held
on a U.S.S. No. 40 sieve (0.42 mm openings) may be
packaged for use and the fines recycled.
Example 9
Solution
N-[(4,6-Dimethylpyrimidin-2-yl~aminocarbonyl]-2-
(methylsulfonyl)-3-pyridinesulfonamide 5%
dimethylformamide 95%
The ingredients are combined and stirred to
produce a solution, which can be used for low-volume
applications.
Example 10
r~ettable Powder
.
N-[(4,6-Dimethylpyrimidin-~-yl)aminocarbonyl]-2-
(methylsulfonyl)-3-pyridinesulfonamide 80%
sodium al~ylnaphthalenesulfona-te 2%
sodium ligninsulfonate 2%
synthetic amorphous silica 3%
kaolinite 13%
x 56
The ingredients are thoroughly blended after
grinding in a hammer mill to produce particles essen-
tially all of which are under 100 microns in size;
the material is reblended, sifted through a U.S.S.
No. 50 sieve and packaged.
Example 11
N-[(4,6-Dimethylpyrimidin-2-yl)aminocaxbonyl]-2-
(methylsulfonyl)-3-pyridinesulfonamide 80
wetting agent 1%
crude ligninsulfonate salt (con-
taining 5-20% of the natural
sugars) 10%
attapulgite clay 9%
The ingredients are blended and milled to pass
through a 100 mesh screen. This material is then
added to a fluid bed granulator, the air f 10W is ad-
justed to gently fluidize the material, and a flne
spray of water is sprayed onto the fluidized material.
The fluidization and spraying are continued until
granules of the desired size range are made. The
spraying is stopped, but fluidization is contlnued,
optionally with heat, until the water content is
reduced to the desired level, generally less than 1%.
The material is then discharged, screened to the de-
sired size range, generally 14-100 mesh (1410-149
microns), and packaged for use.
~L~7~3
x 57
Utility
The compounds of the present invention are
superior herbicides. They have utility for broad-
spectrum pre- and/or post-emergence weed control in
areas where complete control of all vegetation is
desired, such as around fuel storage tanks, ammu-
nition depots, industrial storage areas, parking
lots, drive-in theaters, around billboards, hi~h-
way and railroad structures.
The rates of application for the compounds of
the invention are determined by a number of factors,
including the types of weeds to be controlled, weather
and climate, formulations selected, mode of application,
amount of foliage present, etc. In general terms,
the subject compounds should be applied at levels
of around 0.125 to 10 kg/ha, the lower rates being
suggested for use on liahter soils and/or those
having a low organic matter content, or for situa-
tions where only short-term persistence is required.
The compounds of the invention may be used in
combination with any other commercial herbicide,
examples of which are those of the triazine, tria-
zole, uracil, urea, amide, diphenyl ether, carbamate
and bipyridylium types.
The herbicidal properties of the subject com-
pounds were discovered in a greenhouse test. The
test procedure and results follow.
X ~g
Test Procedure A
Seeds of crabgrass (Digitaria spp.), barn-
yardgrass (~chinocllloa crusgalli), wild oats
(Avena fatua), Cassia tora, morningglory (Ipomoea
spp.), coc~lebur (Xanthium spp.), sorghum, corn,
soybean, rice, wheat as well as nut:sedge tubers
were planted in a growtil medium ancl treated pre-
emergence with the chemicals dissolved in a non-
phytotoxic solvent. At the same time, cotton having
five leaves (including cotyledonary ones), bush beans
with the third trifoliate leaf expanding, crabgrass,
barnyardgrass and wil oats with two leaves, cassia
with three leaves (including cotyledonary ones),
morningglory and cocklebur with four leaves (in-
cluding the cotyledonary ones), sorghum and cornwi-th four leaves, soybean with two cotyledonary
leaves, rice with three leaves, wheat with one leaf,
and nutsedge with three-five leaves were sprayed.
Treated plants and controls were maintained in a
greenhouse for sixteen days, whereupon all species
were compared to controls and visually rated for
response to treatment. The ratings are based on a
numerical scale extending from 0 = no injury, to
lO = complete kill. The accompanying descriptive5 symbols have the following meanings:
G = growth retardation;
C = chlorosis/necrosis;
6Y = abscised buds or flowers;
U = unusual pigmentation;
~ = emergence inhibition; and
H = formative effects.
The ratings for the compound tested by this proce-
dure are presented in Table A.
~9~3
Table A
c~3
(~--S02-NH-C-~3H < 0~
S2CH3 CH3
__ . . _
k~/ha O . 4
- _
POST-EMERGENCE
BUSHBEAN _ 5C,9G!6Y
COTTON 9C
MORNINGGLORY 10C
COCKLEBUR _ -
20 CASSIA = 5C,8G _ _ _
NUTSEDGE 8G
..
CRABGRASS _ 9C
BARNYARDGRASS 7C,9H
WILD OATS -- - 7C
h~EAT 5C,8G
CORN 5U,9G
25 S-OY~ ---- 9C
RICE ~~ 5C,7G
SbRGHUM 9C ~.
PRE-EMERGENCE
_ MORNI~iGGLORY 9G --- -~
COCKLEBUR 9H
CASSIA 9G --
NUTSEDGE 10E ~ ~~~
CRABGRASS _ 2C,9G
BARNYARDGRASS _ _ 9H
. CORN 3C,8H
_
RICE lOE
SORGHUM _ . 5C,9H _ _
