CA1189073A - Pyridyl sulfone herbicides - Google Patents
Pyridyl sulfone herbicidesInfo
- Publication number
- CA1189073A CA1189073A CA000372421A CA372421A CA1189073A CA 1189073 A CA1189073 A CA 1189073A CA 000372421 A CA000372421 A CA 000372421A CA 372421 A CA372421 A CA 372421A CA 1189073 A CA1189073 A CA 1189073A
- Authority
- CA
- Canada
- Prior art keywords
- compound
- aminocarbonyl
- methylsulfonyl
- pyridinesulfonamide
- compounds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/32—One oxygen, sulfur or nitrogen atom
- C07D239/42—One nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyridine Compounds (AREA)
Abstract
Abstract Pyridyl sulfones, e.g., N-[4,6-dimethyl-pyrimidin-2-yl)aminocarbonyl]-2-(methylsulfonyl)-3-pyridinesulfonamide, are useful for the regula-tion of plant growth and as pre-emergence and post-emergence herbicides.
Description
~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.
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) 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 "
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.
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.
3, S02NCS
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;
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;
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.
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) 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 "
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.
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.
3, S02NCS
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;
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.
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:
5. RSO2 ~ ~ ',CN-A -~
N
II
~-~ 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
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.
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:
5. RSO2 ~ ~ ',CN-A -~
N
II
~-~ 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 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)
. ~ N ~ Cl (DMF) ~ N ~ ~ S2CH3 XI XII
1 HONO HCl ~5~ ~NH2 S , CuCl 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
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 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~
XXV
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 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 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 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~
~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_ 2-CH3SO2 H O~N~
2-CE~3 S02 H O~No~
~C~-I3 202-CI13SO2 EI O_( O~
OC~ 3 2-CH3S02 H O~ O~
NV
N~
2-CH3SO2 H O~ o~h N _~C H 3 302-CM3SO2 H ON t (CH3 2-CH3SO2 H O N~
CEI
2-CH3SO2 H O~N~
N ~N - CH3 x 25 Tabl e I ( continued ) 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$0~ H O
N ~ Ci13 2~ CH3 S 2 11 G) cr''I20CH3 c~3 2-CH3SO2 H O N~
CH2CH2C~I3 2-CH3S02 H O N(~
3 0 N ~13 2-CH3S02 H ~NO~
c~3 2-CH3SO2 H O ~ ~
x 26 Tabl e I ( c ont i nued ) F<S02 _ W A
C~l N~ 3 2-CH3S02 H O ~0~
2-CII3S02 H O ~NO~
O ( 3 ) 2 3 2-CH3S02 H O ~N~)$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~
~C~12C02C2~5 OCH (CH3 ) C02C~I3 OC~-' 2-CH3S02 H O N (CH3) 2 x 27 Table I (continued) RSO2 z ~ A
N_~OCH3 2-CH3SO2 H O ~ O~
2-CH3S02 ~1 o <~o$ 3 OC2Hs ,OCH
2~CH3S2 H O ~ O~
_~OCII 3 2-CIi3SO2 H O N~
1 5 C~120CH3 OC~Il '`-Cll SO M Q ~T
CEI2CM2Qe~II3 2-CH3SO2 H O ~ ~Cll3 N-C~i 2CI~
CM
2-CH3S02 H O ~ o~CH3 C ~I 3 2-CII3SO2 H O ~IO~CM2CH3 ~13 2-CH3S02 H O ~ o~ C~12CH2Cl N~
2-CH3SO2 H O ~NO~
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 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 x 29 Table I (continued) 2 _ W A_ ~ OCH3 2-CH3SO2 H O ~NO~
2-CH3SO2 H O ~Jo~) CH2('H20CH3 OCI-I
2-CH3SO2 H O ~ O~
OCH
2-CH3SO2 H ~No~
1 5 OCH~CO~M
OC Ll 2 CH3S2 El (~
I2~ }13 2-CH SO H O ~) OCH2C02C2~[5 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
~L~o~ CH3 x 30 Table I (continued) RSO
~ CH3 2-CH SO H o ~ O~d 3 2 N~
~ ~c~3 2 - CH 3 SO 2 H ~(N~C' 1 0 ~CH3 2-CH3SO2 H O ~NO~
N _~CH3 2-CH3S2 }I ~!?y~
N ~Cii3 2-CH3S02 El O ~N ~
C:li2C0 ~1I
2 0 2 -CI1 3S~)2 1~
_~ CEi3 2-CH3SO2 H O ~NO~
N_~CEi 3 2-CH3S02 H o ~~ O~
OCEI ( H3 ) 2 3 3 0 _~CH3 2-CEI3SO2 H O N~
N(CEI3) 2 3 2 ~NC~) x 31 Tabl e I ( continued ) RS02 z W A
2-CH SO G-Br O ~( ~
2-CH3S02 6-F O~0~ H3 2-CH3S02 6-CH3 ~ ~CEI3 N _~CH 3 2-CH SO 6-CEI30 ~ ~) 2 - C EI 3 S 2 6 - C~3 ~(~
~CI.13 2 -CH 3 SO 2 H SN(~
_~ CEI 3 2-CH3S02 H S<NO-~) H 3 2 S ~
C~I3 3 0 _~CH3 2-CEI3S02 H Si~I ~
7q~
Table I (continued) OC~
~ 3 2-CH SO H S ~ O
3 2 N~
2-CH3CH2SO2 H O CEl3 102-CH3 (CH2) 5SO2 H O N~
N _~CH 3 2-CII2=CHCH2SO2 H O ~r~cH
2~ CEI3 (CEI 2 ) 2CEI=CHCH2SO2 H ~CE3 202-CH30CH2S02 H -(rlb~, ( CII3 2-CH30CH2CH20CH2S02 H O -~~) 3 0 ~_~CEI3 2-C2H5OcH2c~I2OcH2so2 H O N~cH
2-CH3OCH2CH2oCH2CH2So2 ~N~) 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~
104 C 3 2 H O N~
~C~13 4 3 2 H O ~NO~
I`l-~CH3 3 2 H O ~NO~
N ~OCH3 204-CH3sO2 H O ~NO~J
OCrI3 c~3 4-CH3sO2 H O N ~
N~ 3 5-CH3sO2 H O ~NO~
5-CE3sO2 H O ~
N~
5 C 3 2 H O ~NO~
- ~L~7~
x 34 Table I (continued) CH
N~, 3 5-CEI3S02 H 0 -~ 0~
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~) 6--CH3SO2 H O -(N~O~
2 0 ~CIi3 6-CEI3SO2 H O ~NO~
6-CEi3So2 H ~NO~
OC~ 3 6-CH3SO2 H O ~ O~
c~3 2-CH SO2 H O ~ ~) 3 N~
N (CH3) 2 ~8~q3 x 35 Tabl e I ( continued ) i 2- Q H 0 ~NO~H3 2- O~ H 0 ~0~
S02 cHH3 2- ~}S2 H 0 CH3 N _~:H 3 2- Cl~S0,, H (N0~
2 0 M _<CH 3 2- C'H 30~S0 H 0 2- F~so2 H 0 ~p 2- CEI 3~}S02 H o ~NN~)cH3 2- Br ~ S02 H N~CH
2"~ CI~3 2- ~} S02 H 0 ~N~I3 x 36 Tabl e I ( cont inued ?
RSO~
Z 1~ A
~ C~
2- <~ S02 H O~No~ 3 N--(CII 3 Cl CH
2- Cl--~ S02 H O~NIo~ 3 2- ~ 2 2 H O ~CH3 C~I3 2- Cl~CH -SO H ~N~O~33 2- <~ 2 2 2 H O~ 0~) 2- Cl~CH2CEI2-s02 ` H O ~ 0~
2 - CF 3 S 2 H -(NO~') 2-~CF2CF2S2 H O ~CH3 2-HCFClCF2so2 H O~NO~) C~I3 7~
x 37 Tabl e I ( continued ) N ~CH3 2-HCFBrCF2SO2 H O ~ O>
~:II 3 2--CF3E;CFCF2S02 H O ~NO~
2 2 2 H O ~O ~
N _<CH 3 2-H2CFCF2So2 H O ~~) 2 0 M-~C~I 3 2-CF3CH,~S02 H O ~ O~
~ ~89~3 x 3g Table II
~ S02Cl RS 2 ~)~
,7 1~ _ 2-CH3~CH2)SS02 H
2-CH2=CHCH2So2 Ii 2-CH3(CH2)2CH=CHCH2S2 H
2-CH30CH2So2 H
2-C2H50CH2CH2So2 H
2-C2H5CH2C~2CH2S2 H
2-CH30C~I2CH20C~12CH2S02 H
2-c2H5ocH2cH2ocH2c-I2so2 H
2-CIi3S02 6-Cl 2-CH3S02 6-Br 5-CH3s2 H
6-CE3So2 H
2- ~ S2 H
x 39 Table II (continued) 2- ~S02 H
2- Cl ~S02 E;
2- CH30 ~3So2 H
r~
2- F~sQ2 H
2~ CH3~ S02 H
15 2- 3r~}S02 2- 02N~ H
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
~L8~
x 41 Table III
2 ~ S2~H2 RS02 z 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
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
2- O2N~ H
2- CF3 ~ H
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) 5 2-CF3So2 H
2 C 2 S O ~ H
2-HCFClCF2SO2 H
2-HCFBrCF 2 S2 H
2-CF3HCFCF2So2 H
2-H2CFCF2So2 EI
2-CF3CH2So2 H
x 44 Table IV
,~ so2NCO
RS02 ~ ~
RS02 z 2-CH3So2 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
2-C2H50CH2CH20cH2c~2s02 H
2-CIi3S02 6-Cl 2-C~3S02 6-Br 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
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) . .
5 2-CF3So2 H
2-HCF2CF2So2 H
2-HCFClCF~SO2 H
2-HCFBrCF2SO2 H
2-CF3HCFCF2So2 H
2-H2CFCF2So2 EI
2-CF3CH2So2 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
3 CH2C120CE12CH2So2 H
2-c2H5ocH2cH2ocH2cI2so2 H
2-CIi3S02 6-Cl 2-CH3S02 6-Br 2-CH3So2 6-CH3 2-CH3So2 6-CH3S
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
2- O2N ~ H
2- CF3-~ H
2- C1~} S02 H
2- ~} CH2S02 H
2- Cl~CH2SO2 EI
2- ~CH2CH2SO2 H
35 2- C1~ CH2CH2SO2 H
~73 Table V (continued) 2-HCF2CF2So2 H
2 -HCFClCF 2 S2 H
2-HCFBrCF2SO2 H
2-CF3HCFCF2So2 H
2-H2CFCF2So2 H
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%
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.
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 descriptive 5 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~
__ . . _ k~/ha O . 4 - _ POST-EMERGENCE
BUSHBEAN _ 5C,9G!6Y
COCKLEBUR _ -20 CASSIA = 5C,8G _ _ _ ..
CRABGRASS _ 9C
BARNYARDGRASS 7C,9H
h~EAT 5C,8G
CORN 5U,9G
25 S-OY~ ---- 9C
RICE ~~ 5C,7G
SbRGHUM 9C ~.
PRE-EMERGENCE
_ MORNI~iGGLORY 9G --- -~
NUTSEDGE 10E ~ ~~~
CRABGRASS _ 2C,9G
BARNYARDGRASS _ _ 9H
. CORN 3C,8H
_ RICE lOE
SORGHUM _ . 5C,9H _ _
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
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 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~
XXV
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 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 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 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~
~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_ 2-CH3SO2 H O~N~
2-CE~3 S02 H O~No~
~C~-I3 202-CI13SO2 EI O_( O~
OC~ 3 2-CH3S02 H O~ O~
NV
N~
2-CH3SO2 H O~ o~h N _~C H 3 302-CM3SO2 H ON t (CH3 2-CH3SO2 H O N~
CEI
2-CH3SO2 H O~N~
N ~N - CH3 x 25 Tabl e I ( continued ) 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$0~ H O
N ~ Ci13 2~ CH3 S 2 11 G) cr''I20CH3 c~3 2-CH3SO2 H O N~
CH2CH2C~I3 2-CH3S02 H O N(~
3 0 N ~13 2-CH3S02 H ~NO~
c~3 2-CH3SO2 H O ~ ~
x 26 Tabl e I ( c ont i nued ) F<S02 _ W A
C~l N~ 3 2-CH3S02 H O ~0~
2-CII3S02 H O ~NO~
O ( 3 ) 2 3 2-CH3S02 H O ~N~)$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~
~C~12C02C2~5 OCH (CH3 ) C02C~I3 OC~-' 2-CH3S02 H O N (CH3) 2 x 27 Table I (continued) RSO2 z ~ A
N_~OCH3 2-CH3SO2 H O ~ O~
2-CH3S02 ~1 o <~o$ 3 OC2Hs ,OCH
2~CH3S2 H O ~ O~
_~OCII 3 2-CIi3SO2 H O N~
1 5 C~120CH3 OC~Il '`-Cll SO M Q ~T
CEI2CM2Qe~II3 2-CH3SO2 H O ~ ~Cll3 N-C~i 2CI~
CM
2-CH3S02 H O ~ o~CH3 C ~I 3 2-CII3SO2 H O ~IO~CM2CH3 ~13 2-CH3S02 H O ~ o~ C~12CH2Cl N~
2-CH3SO2 H O ~NO~
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 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 x 29 Table I (continued) 2 _ W A_ ~ OCH3 2-CH3SO2 H O ~NO~
2-CH3SO2 H O ~Jo~) CH2('H20CH3 OCI-I
2-CH3SO2 H O ~ O~
OCH
2-CH3SO2 H ~No~
1 5 OCH~CO~M
OC Ll 2 CH3S2 El (~
I2~ }13 2-CH SO H O ~) OCH2C02C2~[5 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
~L~o~ CH3 x 30 Table I (continued) RSO
~ CH3 2-CH SO H o ~ O~d 3 2 N~
~ ~c~3 2 - CH 3 SO 2 H ~(N~C' 1 0 ~CH3 2-CH3SO2 H O ~NO~
N _~CH3 2-CH3S2 }I ~!?y~
N ~Cii3 2-CH3S02 El O ~N ~
C:li2C0 ~1I
2 0 2 -CI1 3S~)2 1~
_~ CEi3 2-CH3SO2 H O ~NO~
N_~CEi 3 2-CH3S02 H o ~~ O~
OCEI ( H3 ) 2 3 3 0 _~CH3 2-CEI3SO2 H O N~
N(CEI3) 2 3 2 ~NC~) x 31 Tabl e I ( continued ) RS02 z W A
2-CH SO G-Br O ~( ~
2-CH3S02 6-F O~0~ H3 2-CH3S02 6-CH3 ~ ~CEI3 N _~CH 3 2-CH SO 6-CEI30 ~ ~) 2 - C EI 3 S 2 6 - C~3 ~(~
~CI.13 2 -CH 3 SO 2 H SN(~
_~ CEI 3 2-CH3S02 H S<NO-~) H 3 2 S ~
C~I3 3 0 _~CH3 2-CEI3S02 H Si~I ~
7q~
Table I (continued) OC~
~ 3 2-CH SO H S ~ O
3 2 N~
2-CH3CH2SO2 H O CEl3 102-CH3 (CH2) 5SO2 H O N~
N _~CH 3 2-CII2=CHCH2SO2 H O ~r~cH
2~ CEI3 (CEI 2 ) 2CEI=CHCH2SO2 H ~CE3 202-CH30CH2S02 H -(rlb~, ( CII3 2-CH30CH2CH20CH2S02 H O -~~) 3 0 ~_~CEI3 2-C2H5OcH2c~I2OcH2so2 H O N~cH
2-CH3OCH2CH2oCH2CH2So2 ~N~) 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~
104 C 3 2 H O N~
~C~13 4 3 2 H O ~NO~
I`l-~CH3 3 2 H O ~NO~
N ~OCH3 204-CH3sO2 H O ~NO~J
OCrI3 c~3 4-CH3sO2 H O N ~
N~ 3 5-CH3sO2 H O ~NO~
5-CE3sO2 H O ~
N~
5 C 3 2 H O ~NO~
- ~L~7~
x 34 Table I (continued) CH
N~, 3 5-CEI3S02 H 0 -~ 0~
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~) 6--CH3SO2 H O -(N~O~
2 0 ~CIi3 6-CEI3SO2 H O ~NO~
6-CEi3So2 H ~NO~
OC~ 3 6-CH3SO2 H O ~ O~
c~3 2-CH SO2 H O ~ ~) 3 N~
N (CH3) 2 ~8~q3 x 35 Tabl e I ( continued ) i 2- Q H 0 ~NO~H3 2- O~ H 0 ~0~
S02 cHH3 2- ~}S2 H 0 CH3 N _~:H 3 2- Cl~S0,, H (N0~
2 0 M _<CH 3 2- C'H 30~S0 H 0 2- F~so2 H 0 ~p 2- CEI 3~}S02 H o ~NN~)cH3 2- Br ~ S02 H N~CH
2"~ CI~3 2- ~} S02 H 0 ~N~I3 x 36 Tabl e I ( cont inued ?
RSO~
Z 1~ A
~ C~
2- <~ S02 H O~No~ 3 N--(CII 3 Cl CH
2- Cl--~ S02 H O~NIo~ 3 2- ~ 2 2 H O ~CH3 C~I3 2- Cl~CH -SO H ~N~O~33 2- <~ 2 2 2 H O~ 0~) 2- Cl~CH2CEI2-s02 ` H O ~ 0~
2 - CF 3 S 2 H -(NO~') 2-~CF2CF2S2 H O ~CH3 2-HCFClCF2so2 H O~NO~) C~I3 7~
x 37 Tabl e I ( continued ) N ~CH3 2-HCFBrCF2SO2 H O ~ O>
~:II 3 2--CF3E;CFCF2S02 H O ~NO~
2 2 2 H O ~O ~
N _<CH 3 2-H2CFCF2So2 H O ~~) 2 0 M-~C~I 3 2-CF3CH,~S02 H O ~ O~
~ ~89~3 x 3g Table II
~ S02Cl RS 2 ~)~
,7 1~ _ 2-CH3~CH2)SS02 H
2-CH2=CHCH2So2 Ii 2-CH3(CH2)2CH=CHCH2S2 H
2-CH30CH2So2 H
2-C2H50CH2CH2So2 H
2-C2H5CH2C~2CH2S2 H
2-CH30C~I2CH20C~12CH2S02 H
2-c2H5ocH2cH2ocH2c-I2so2 H
2-CIi3S02 6-Cl 2-CH3S02 6-Br 5-CH3s2 H
6-CE3So2 H
2- ~ S2 H
x 39 Table II (continued) 2- ~S02 H
2- Cl ~S02 E;
2- CH30 ~3So2 H
r~
2- F~sQ2 H
2~ CH3~ S02 H
15 2- 3r~}S02 2- 02N~ H
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
~L8~
x 41 Table III
2 ~ S2~H2 RS02 z 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
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
2- O2N~ H
2- CF3 ~ H
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) 5 2-CF3So2 H
2 C 2 S O ~ H
2-HCFClCF2SO2 H
2-HCFBrCF 2 S2 H
2-CF3HCFCF2So2 H
2-H2CFCF2So2 EI
2-CF3CH2So2 H
x 44 Table IV
,~ so2NCO
RS02 ~ ~
RS02 z 2-CH3So2 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
2-C2H50CH2CH20cH2c~2s02 H
2-CIi3S02 6-Cl 2-C~3S02 6-Br 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
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) . .
5 2-CF3So2 H
2-HCF2CF2So2 H
2-HCFClCF~SO2 H
2-HCFBrCF2SO2 H
2-CF3HCFCF2So2 H
2-H2CFCF2So2 EI
2-CF3CH2So2 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
3 CH2C120CE12CH2So2 H
2-c2H5ocH2cH2ocH2cI2so2 H
2-CIi3S02 6-Cl 2-CH3S02 6-Br 2-CH3So2 6-CH3 2-CH3So2 6-CH3S
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
2- O2N ~ H
2- CF3-~ H
2- C1~} S02 H
2- ~} CH2S02 H
2- Cl~CH2SO2 EI
2- ~CH2CH2SO2 H
35 2- C1~ CH2CH2SO2 H
~73 Table V (continued) 2-HCF2CF2So2 H
2 -HCFClCF 2 S2 H
2-HCFBrCF2SO2 H
2-CF3HCFCF2So2 H
2-H2CFCF2So2 H
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%
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.
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 descriptive 5 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~
__ . . _ k~/ha O . 4 - _ POST-EMERGENCE
BUSHBEAN _ 5C,9G!6Y
COCKLEBUR _ -20 CASSIA = 5C,8G _ _ _ ..
CRABGRASS _ 9C
BARNYARDGRASS 7C,9H
h~EAT 5C,8G
CORN 5U,9G
25 S-OY~ ---- 9C
RICE ~~ 5C,7G
SbRGHUM 9C ~.
PRE-EMERGENCE
_ MORNI~iGGLORY 9G --- -~
NUTSEDGE 10E ~ ~~~
CRABGRASS _ 2C,9G
BARNYARDGRASS _ _ 9H
. CORN 3C,8H
_ RICE lOE
SORGHUM _ . 5C,9H _ _
Claims (22)
1. A compound selected from:
wherein R is C1-C6 alkyl, C3-C6 alkenyl, C2-C4 alkoxyalkyl, C5-C6 cycloalkyl, R1OCH2CH20CH2, R1OCH2CH2OCH2CH2, R1 is methyl or ethyl;
R2 and R3 are independently H, C1, OCH3, F, CH3, Br, NO2 or CF3;
n is 0, 1 or 2;
G is F, C1, Br or CF3;
L is F, C1 or H;
Z is H, F, C1, Br, CH3, CH3O or CH3S;
W is O or S;
A is X is CH3 or CH3O;
Y is CH3, CH3CH2, CH3O, CH3CH2O, CF3CH2O, CH3O(CH2)m, CH3OCH2CH2O' , (CH3)2N or CH3NCH2CN;
E is CH, N, C-CH3, C-CH2CH3 or C-CH2CH2Cl;
R4 is H, CH3 or CH3CH2;
R5 is H or CH3;
m is 1 or 2;
X' is H, CH3, CH3O or Cl; and Y' is O or CH2;
and their agriculturally suitable salts.
wherein R is C1-C6 alkyl, C3-C6 alkenyl, C2-C4 alkoxyalkyl, C5-C6 cycloalkyl, R1OCH2CH20CH2, R1OCH2CH2OCH2CH2, R1 is methyl or ethyl;
R2 and R3 are independently H, C1, OCH3, F, CH3, Br, NO2 or CF3;
n is 0, 1 or 2;
G is F, C1, Br or CF3;
L is F, C1 or H;
Z is H, F, C1, Br, CH3, CH3O or CH3S;
W is O or S;
A is X is CH3 or CH3O;
Y is CH3, CH3CH2, CH3O, CH3CH2O, CF3CH2O, CH3O(CH2)m, CH3OCH2CH2O' , (CH3)2N or CH3NCH2CN;
E is CH, N, C-CH3, C-CH2CH3 or C-CH2CH2Cl;
R4 is H, CH3 or CH3CH2;
R5 is H or CH3;
m is 1 or 2;
X' is H, CH3, CH3O or Cl; and Y' is O or CH2;
and their agriculturally suitable salts.
2. Compounds of Claim 1 wherein the sub-stituent RSO2 is at the 2-position of the pyridine ring.
3. Compounds of Claim 2 wherein W is O.
4. Compounds of Claim 3 wherein Z is H.
5. Compounds of Claim 4 wherein R is C1-C4 alkyl.
6. Compounds of Claim 5 wherein Y is CH3, CH3O or CH3CH2O.
7. Compounds of Claim 6 wherein E is CH or N.
8. The compound of Claim 1, N-[(4,6-dimethyl-pyrimidin-2-yl)aminocarbonyl]-2-(methylsulfonyl)-3-pyridinesulfonamide.
9. The compound of Claim 1, N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-(methylsulfonyl)-3-pyridinesulfonamide.
10. The compound of Claim 1, N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-2-(methylsulfonyl)-3-pyridinesulfonamide.
11. The compound of Claim 1, N-[(4,6-dimethoxy-pyrimidin-2-yl)aminocarbonyl]-2-(methylsulfonyl)-3-pyridinesulfonamide.
12. The compound of Claim 1, N-[(4,6-dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-(methylsulfonyl)-3-pyridinesulfonamide.
13. The compound of Claim 1, N- [(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-(methyl-sulfonyl)-3-pyridinesulfonamide.
14. The compound of Claim 1, N-[(6,7-dihydro-4-methyl-5H-cyclopentapyrimidin-2-yl)aminocarbonyl]-2-(methylsulfonyl)-3-pyridinesulfonamide.
15. The compound of Claim 1, N-[(6,7-dihydro-4-methoxy-5H-cyclopentapyrimidin-2-yl)aminocarbonyl]-2-(methylsulfonyl)-3-pyridinesulfonamide.
16. The compound of Claim 1, N-[(5,6-dihydro-4-methylfuro[2,3-D]pyrimidin-2-yl)aminocarbonyl]-2-(methylsulfonyl)-3-pyridinesulfonamide.
17. The compound of Claim 1, N-[(5,6-dihydro-4-methoxyfuro[2,3-D]pyrimidin-2-yl)aminocarbonyl]-2-(methylsulfonyl)-3-pyridinesulfonamide.
18. A method for the control of undesirable vegetation comprising applying to the locus of such undesirable vegetation a herbicidally effective amount of a compound of Claim 1.
19. A method for the control of undesirable vegetation comprising applying to the locus of such undesirable vegetation a herbicidally effective amount of a compound of Claim 2.
20. A method for the control of undesirable vegetation comprising applying to the locus of such undesirable vegetation a herbicidally effective amount of a compound of Claim 3.
21. A method for the control of undesirable vegetation comprising applying to the locus of such undesirable vegetation a herbicidally effective amount of a compound of Claim 4.
22. A method for the control of undesirable vegetation comprising applying to the locus of such undesirable vegetation a herbicidally effective amount of the compound of Claim 5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12817680A | 1980-03-07 | 1980-03-07 | |
| US128,176 | 1980-03-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1189073A true CA1189073A (en) | 1985-06-18 |
Family
ID=22434023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000372421A Expired CA1189073A (en) | 1980-03-07 | 1981-03-05 | Pyridyl sulfone herbicides |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS56139466A (en) |
| KR (1) | KR830005165A (en) |
| CA (1) | CA1189073A (en) |
| PH (1) | PH17301A (en) |
| ZA (1) | ZA811484B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4618363A (en) * | 1982-01-25 | 1986-10-21 | Ciba-Geigy Corporation | N-phenylsulfonyl-N'-triazinylureas |
| ZA836639B (en) * | 1982-09-08 | 1984-05-30 | Ciba Geigy Ag | Novel sulfonylureas |
| JPS6036386A (en) * | 1983-08-05 | 1985-02-25 | 東芝セラミツクス株式会社 | Filler for sliding nozzle |
| JP2546200B2 (en) * | 1991-02-20 | 1996-10-23 | 東ソー株式会社 | Aqueous suspension formulation and spraying method for weeding before paddy field |
| JP5468289B2 (en) | 2008-04-18 | 2014-04-09 | 石原産業株式会社 | Method for producing pyrimidine compounds |
-
1981
- 1981-03-05 CA CA000372421A patent/CA1189073A/en not_active Expired
- 1981-03-05 JP JP3063181A patent/JPS56139466A/en active Pending
- 1981-03-05 PH PH25317A patent/PH17301A/en unknown
- 1981-03-05 ZA ZA00811484A patent/ZA811484B/en unknown
- 1981-03-07 KR KR1019810000751A patent/KR830005165A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ZA811484B (en) | 1982-10-27 |
| KR830005165A (en) | 1983-08-03 |
| PH17301A (en) | 1984-07-18 |
| JPS56139466A (en) | 1981-10-30 |
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