TREA

N-pyridinyl[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide herbicides

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Information

  • Patent Grant
  • 5614469
  • Patent Number
    5,614,469
  • Date Filed
    Tuesday, June 6, 1995
    29 years ago
  • Date Issued
    Tuesday, March 25, 1997
    27 years ago
Information
Abstract
Substituted N-pyridinyl[1,2,4]triazolo[1,5-c]-pyrimidine-2-sulfonamide compounds, such as N-(2-fluoro-4-methyl)-7-fluoro-5-methoxy[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide, were prepared bycondensation of a 2-chlorosulfonyl[1,2,4]triazolo[1,5-c]pyrimidine compound, such as 2-chlorosulfonyl-7-fluoro-5-methoxy[1,2,4]triazolo[1,5-c]pyrimidine, with a substituted 3-aminopyridine compound, such as 3-amino-2-fluoro-4-methylpyridine, and found to possess herbicidal utility.
Description

BACKGROUND OF THE INVENTION
The present invention relates to substituted sulfonamide compounds, to herbicidal compositions containing the compounds, and to the utility of the compounds for the control of unwanted vegetation.
The control of unwanted vegetation by means of chemical agents, i.e., herbicides, is an important aspect of modern agriculture and land management. While many chemicals that are useful for the control of unwanted vegetation are known, new compounds that are more effective generally, are more effective for specific plant species, are less damaging to desirable vegetation, are safer to man or the environment, are less expensive to use, or have other advantageous attributes are desirable.
A number of sulfonamide compounds, including certain substituted [1,2,4]triazolo[1,5-a]pyrimidine-2-sulfonamide compounds (U.S. Pat. No. 4,954,163) and [1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide compounds (U.S. Pat. No. 5,010,195 and European Application 244,948), are known to possess herbicidal activity, especially on broadleaf weeds.
SUMMARY OF THE INVENTION
It has now been found that certain N-pyridinyl[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide compounds are potent herbicides for the control of unwanted vegetation, have desirable crop selectivity, and have favorable toxicological and environmental attributes. The compounds are effective on grassy as well as broadleaf weeds.
The invention includes N-pyridinyl[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide compounds of Formula I: ##STR1## wherein
R represents CH.sub.2 CF.sub.3 or (C.sub.1 -C.sub.3)alkyl optionally monosubstituted with F, Cl, or OCH.sub.3 ;
Y and Z each independently represents H, F, Cl, Br, in, OCH.sub.3, OC.sub.2 H.sub.5, C.sub.2 H.sub.5 or CH.sub.3 optionally mono to completely substituted with F;
V represents H, COR', CO.sub.2 R", or CONR"'.sub.2 ;
A and B each independently represents H, R', OR', OCH.sub.2 CH.sub.2 Cl, OCH.sub.2 CH.sub.2 OCH.sub.3, S(O).sub.n R', P, Cl, Br, I, CN, NO.sub.2, C.sub.6 H.sub.5, CO.sub.2 R", or CONR'".sub.2 with the proviso that not more than one of A and B represents H;
D represents H, F, Cl, Br, I, CF.sub.3, or CH.sub.3 ;
n represents 0, 1, or 2;
R'represents (C.sub.1 -C.sub.4)alkyl optionally singly to completely substituted with fluorine;
R" represents (C.sub.1 -C.sub.4)alkyl, (C.sub.3 -C.sub.4)alkenyl, or (C.sub.3 -C.sub.4) alkynyl,
R"' represents H or (C.sub.1 -C.sub.4) alkyl; and when V represents H, the agriculturally acceptable salts thereof.
The compounds of the invention, usually in the form of an herbicidal composition containing one or more of them in admixture with an agriculturally acceptable adjuvant or carrier, exhibit strong herbicidal properties when applied either directly to the unwanted vegetation or to the locus thereof and when applied either preemergence or postemergence.





DETAILED DESCRIPTION OF THE INVENTION
The N-pyridinyl[1,2,4]triazolo[1,5-c]-myrimidine-2-sulfonamide compounds of the invention can be characterized as [1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide compounds possessing an alkoxy substituent in the 5-position, alkyl, substituted alkyl, alkoxy, or halogen substituents in either or both of the 7- and 8-positions, and a substituted 3-pyridinyl moiety on the sulfonamide nitrogen atom. They are amides derived from a substituted [1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonic acid compound and a substituted 3-aminopyridine compound.
The compounds of the invention include those of Formula I: ##STR2## wherein R represents methyl, ethyl, propyl, 1-methylethyl, or cyclopropyl, each optionally monosubstituted with fluorine, chlorine or methoxy or represents 2,2,2-trifluoroethyl. Methyl and ethyl are typically preferred.
The Y and Z substituents of Formula I are independently selected and include hydrogen, methyl optionally mono to completely substituted with fluorine, or ethyl, fluoro, chloro, bromo, iodo, methoxy, or ethoxy. The substituents H, CH.sub.3, F, Cl, Br, I, and OCH.sub.3 are typically preferred and compounds wherein one of Y and Z represents F, Cl, Br, I, CH.sub.3, or OCH.sub.3 and the other represents H are often more preferred. Compounds wherein R represents methyl or ethyl, Y represents methyl, and Z represents hydrogen or wherein R represents methyl or ethyl, Y represents hydrogen, and Z represents a halogen or methoxy are often of special interest.
The term V in Formula I generally represents hydrogen, CO(C.sub.1 -C.sub.4)alkyl optionally singly to completely substituted with fluorine, CO.sub.2 (C.sub.1 -C.sub.4)alkyl, CO.sub.2 (C.sub.3 -C.sub.4)alkenyl, CO.sub.2 (C.sub.3 -C.sub.4)alkynyl, CONH.sub.2, CONH(C.sub.1 -C.sub.4)alkyl, or CON((C.sub.1 -C.sub.4)alkyl).sub.2. Hydrogen is typically preferred.
Substituents A and B on the pyridine ring of the compounds of Formula I independently represent hydrogen, fluoro, chloro, bromo, iodo, cyano, nitro, phenyl, 2-chloroethyl, 2-methoxyethyl, CO.sub.2 (C.sub.1 -C.sub.4)alkyl, CO.sub.2 (C.sub.3 -C.sub.4) alkenyl, or CO.sub.2 (C.sub.3 -C.sub.4)alkynyl, CONH.sub.2, CONH(C.sub.1 -C.sub.4)alkyl, or CON((C.sub.1 -C.sub.4)alkyl) 2, or represent (C.sub.1 -C.sub.4)alkyl, (C.sub.1 -C.sub.4)alkoxy, (C.sub.1 -C.sub.4)alkylthio, (C.sub.1 -C.sub.4)alkylsulfinyl, or (C.sub.1 -C.sub.4) alkylsulfonyl each optionally singly to completely substituted with fluorine, provided that at least one of A and B represents a substituent other than hydrogen. It is usually preferable that A and B both represent a substituent other than hydrogen. Methyl, ethyl, hydrogen, methoxy, ethoxy, propoxy, 1-methylethoxy, 1-methyl-2,2,2-trifluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, methoxycarbonyl, ethoxycarbonyl, fluoro, chloro, and bromo are often preferred substituents. The term D represents hydrogen, fluoro, chloro, bromo, iodo, trifluoromethyl, or methyl. It is often preferably hydrogen or methyl and is usually more preferably hydrogen. Compounds wherein A represents CH.sub.3, O(C.sub.1 -C.sub.3)alkyl, F, Cl, Br, or I; B represents F, Cl, Br, I, CH.sub.3, C.sub.2 H.sub.5, CF.sub.3, O(C.sub.1 -C.sub.3)alkyl, OCH(CH.sub.3)CF.sub.3, OCH.sub.2 CH.sub.2 F, OCH.sub.2 CHF.sub.2, or CO.sub.2 (C.sub.1 -C.sub.3)alkyl; and D represents H are often preferred. Compounds wherein A represents Br, Cl, F, or OCH.sub.3, B represents CH.sub.3, OCH.sub.3, OC.sub.2 H.sub.5, OC.sub.3 H.sub.7 (n), OC.sub.3 H.sub.7 (i), OCH(CH.sub.3)CF.sub.3, or OCH.sub.2 CH.sub.2 F, and D represents H; or wherein A represents OCH.sub.3 or OC.sub.2 H.sub.5, B represents CO.sub.2 (C.sub.1 -C.sub.2)alkyl, Br, Cl, or F, and D represents H are sometimes of special interest.
When V represents hydrogen, the compounds of Formula I are acidic and the invention includes the agriculturally acceptable salts.
The term alkyl as used herein includes straight chain, branched chain, and cyclic moieties. Thus, typical alkyl groups are methyl, ethyl, 1-methylethyl, propyl, cyclopropyl and the like. Methyl and ethyl are often preferred. Typical alkyl groups singly to completely substituted with fluorine include trifluoromethyl, monofluoromethyl, 2,2,2-trifluoroethyl, 2,3-difluoropropyl, and the like; trifluoromethyl is often preferred. Typical alkyl groups monosubstituted with methoxy or chloro include 2-chloroethyl, methoxymemhyl, and 2-methoxy-1-methylethyl.
The term "agriculturally acceptable salts" is employed herein to denote compounds wherein the acidic sulfonamide proton of the compound of Formula I is replaced by a cation which itself is neither herbicidal to crop plants being treated nor significantly deleterious to the applicator, the environment, or the ultimate user of any crop being treated. Suitable cations include, for example, those derived from alkali or alkaline earth metals and those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium, and aminium cations of the formula:
R.sup.6 R.sup.7 R.sup.8 NH.sup..sym.
wherein R.sup.6, R.sup.7, and R.sup.8 each, independently represents hydrogen or (C.sub.1 -C.sub.12)alkyl, (C.sub.3 -C.sub.12)cycloalkyl, or (C.sub.3 -C.sub.12)alkenyl, each of which is optionally substituted by one or more hydroxy, (C.sub.1 -C.sub.8)alkoxy, (C.sub.1 -C.sub.8)alkylthio or phenyl groups; provided that R.sup.6, R.sup.7, and R.sup.8 are sterically compatible. Additionally, any two of R.sup.6, R.sup.7, and R.sup.8 together may represent an aliphatic difunctional moiety containing 1 to 12 carbon atoms and up to two oxygen or sulfur atoms. Salts of the compounds of Formula I can be prepared by treatment of compounds of Formula I wherein V represents hydrogen with a metal hydroxide, such as sodium hydroxide, potassium hydroxide, or magnesium hydroxide, or an amine, such as ammonia, trimethylamine, hydroxyethylamine, bisallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine, or benzylamine.
A listing of some typical compounds of the invention is given in Table 1. Some of the specifically preferred compounds of the invention include the following: N-(2-fluoro-4-methyl-3-pyridinyl)-5,8-dimethoxy[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide, N-(2-chloro-4-methoxy-3-pyridinyl)-5-methoxy-7-methyl[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide, N-(2-methoxy-4-methyl-3-pyridinyl)-7-fluoro-5-methoxy[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide, N-(2-chloro-4-methoxy-3-pyridinyl)-7-fluoro-5-methoxy[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide, N-(2-chloro-4-methyl-3-pyridinyl)-8-iodo-5-methoxy[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide, N-(2-chloro-4-methyl-3-pyridinyl)-8-fluoro-5-methoxy[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide, N-(2-chloro-4-methoxy-3-pyridinyl)-7-chloro-5-ethoxy[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide, N-(2-chloro-4-methyl-3-pyridinyl)-5-methoxy-8-chloro[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide, N-(2-chloro-4-methoxy-3-pyridinyl)-5-ethoxy-7-methyl[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide, and N-(2-chloro-4-(1-methylethoxy-3-pyridinyl)-5-ethoxy-7-methyl[1,2,4]triazolo [1,5-c]pyrimidine-2-sulfonamide.
TABLE 1__________________________________________________________________________N-PYRIDINYL[1,2,4]TRIAZOLO[1,5-C]PYRIMIDINE-2-SULFONAMIDE COMPOUNDS ##STR3## % C % H % N % SCpd. Melting calc. calc. calc. calc.No. R Y Z A B D Form point, .degree.C. found found found found__________________________________________________________________________ 1 C.sub.2 H.sub.5 H OCH.sub.3 Cl H H white 225-226 40.6 3.41 21.8 8.33 powder 40.3 3.61 21.5 8.12 2 C.sub.2 H.sub.5 F H Cl H H white 193-194 38.6 2.70 22.5 8.60 crystals (d) 38.7 2.69 22.4 8.73 3 CH.sub.3 H OCH.sub.3 CO.sub.2 CH.sub.3 H H white 187-189 42.6 3.58 21.3 8.13 powder 42.4 3.53 21.3 8.11 4 CH.sub.3 H I Cl H H solid 197-200 25.4 1.38 17.4 7.97 (d) 26.0 1.30 17.3 7.50 5 CH.sub.3 H I CO.sub.2 CH.sub.3 H H pale yellow 183-186 31.9 2.26 17.1 6.54 powder (d) 32.2 2.28 17.2 6.79 6 C.sub.2 H.sub.5 F H CO.sub.2 CH.sub.3 H H white 182-183 42.4 3.31 21.2 8.09 powder 42.4 3.35 21.2 7.94 7 CH.sub.3 CH.sub.3 H CO.sub.2 CH.sub.3 H H white 181-182 44.4 3.72 22.2 8.47 powder 44.7 3.68 22.5 8.12 8 CH.sub.3 H OCH.sub.3 H CO.sub.2 CH.sub.3 H dihyrate >300(d) 39.0 4.22 19.5 7.45 yellow 38.8 3.52 19.3 6.97 powder 9 C.sub.2 H.sub.5 F H H CO.sub.2 CH.sub.3 H white 141-143 42.4 3.30 21.2 8.09 powder 42.3 3.43 21.0 7.8710 C.sub.2 H.sub.5 F H Cl CO.sub.2 CH.sub.3 H tan powder 191-192 39.0 2.80 19.5 7.44 (d) 39.1 3.00 18.7 6.7811 CH.sub.3 H OCH.sub.3 Cl CO.sub.2 CH.sub.3 H tan powder 214-216 39.2 3.06 19.6 7.48 (d) 39.5 2.97 19.7 7.2812 CH.sub.3 H I Cl CO.sub.2 CH.sub.3 H white 193-194 29.8 1.92 16.0 6.11 powder (d) 30.2 1.83 16.2 6.0613 CH.sub.3 H OCH.sub.3 Cl CH.sub.3 H off-white 196-199 40.5 3.40 21.8 8.32 solid (d) 40.6 3.62 21.9 8.1114 C.sub.2 H.sub.5 F H Cl CH.sub.3 H white solid 177-179 40.4 3.13 21.7 8.29 (d) 40.6 3.20 21.7 8.0315 CH.sub.3 H OCH.sub.3 F CH.sub.3 H white 217-218 42.3 3.55 22.8 8.68 powder (d) 42.5 3.50 22.6 8.8416 CH.sub.3 H I Cl CH.sub.3 H white 203-205 30.0 2.10 17.5 6.67 powder 30.2 2.13 17.1 6.3917 CH.sub.3 H CH.sub.3 Cl CH.sub.3 H pale yellow 207-208 42.3 3.55 22.8 8.69 powder (d) 42.2 3.40 22.5 8.4218 CH.sub.3 Cl H Cl CH.sub.3 H pale yellow 193-194 37.0 2.59 21.6 8.23 powder (d) 37.1 2.44 21.3 8.1419 CH.sub.3 H Cl Cl CH.sub.3 H white 212-214 37.0 2.59 21.6 8.23 powder (d) 37.2 2.46 21.6 8.0120 C.sub.2 H.sub.5 F H F CH.sub.3 H white 188-189 42.2 3.27 22.7 8.66 powder (d) 42.4 3.33 22.6 8.8321 CH.sub.3 CH.sub.3 H Cl CH.sub.3 H white 200-201 42.3 3.55 22.8 8.69 powder (d) 42.4 3.42 22.5 8.7922 CH.sub.3 H F Cl CH.sub.3 H white 203-204 38.7 2.70 22.5 8.60 powder (d) 38.7 2.72 22.3 8.6823 CH.sub.3 H H Cl CH.sub.3 H white 199-201 40.6 3.13 23.7 9.04 powder (d) 40.6 3.12 23.5 8.7824 CH.sub.3 H Cl F CH.sub.3 H white 204-205 38.7 2.90 22.5 8.60 powder (d) 38.5 3.12 22.4 8.2925 CH.sub.3 Cl H F CH.sub.3 H white 182-183 38.7 2.90 22.5 8.60 powder (d) 38.6 2.70 22.3 8.4926 CH.sub.3 H F F CH.sub.3 H tan powder 190-192 40.4 2.83 23.6 9.00 (d) 40.4 3.15 23.6 8.7527 CH.sub.3 CH.sub.3 H F CH.sub.3 H white 194-195 44.3 3.72 23.9 9.10 powder (d) 44.4 3.74 24.1 9.2728 CH.sub.3 H OCH.sub.3 Cl OCH.sub.3 H white 196-197 39.0 3.27 21.0 8.00 powder (d) 39.2 3.34 20.8 7.9029 CH.sub.3 H I F CH.sub.3 H white 194-196 30.9 2.16 18.0 6.86 powder (d) 31.0 2.36 18.0 6.6030 C.sub.2 H.sub.5 F H Cl OCH.sub.3 H white 176-178 38.8 3.00 20.9 7.96 powder (d) 38.6 2.95 20.8 7.9031 CH.sub.3 H OCH.sub.3 Cl Cl H white 215-216 35.6 2.49 20.7 7.91 powder (d) 35.6 2.75 20.5 7.6232 C.sub.2 H.sub.5 F H Cl Cl H white 196-197 35.4 2.23 20.6 7.87 powder (d) 35.6 2.61 20.3 7.4533 CH.sub.3 H CH.sub.3 F CH.sub.3 H white 206-207 44.3 3.72 23.9 9.10 powder (d) 44.5 3.58 24.1 9.3834 CH.sub.3 H H F CH.sub.3 H white 194-195 42.6 3.28 24.8 9.48 powder (d) 42.6 3.39 24.8 9.8335 CH.sub.3 CH.sub.3 H Cl OCH.sub.3 H white solid 195-196 40.6 3.41 21.8 8.33 (d) 40.8 3.59 21.7 8.0836 CH.sub.3 F H OCH.sub.3 CH.sub.3 H white 177-178 42.4 3.56 22.4 8.70 powder (d) 42.3 3.64 22.8 7.9237 CH.sub.3 H OCH.sub.3 OCH.sub.3 CH.sub.3 H white 192-193 44.2 4.24 22.1 8.43 powder 44.2 4.41 22.1 8.4338 CH.sub.3 F H Cl CH.sub.3 H white 170-175 38.7 2.70 22.6 8.60 powder (d) 38.8 2.76 21.3 7.9339 CH.sub.3 H I OCH.sub.3 CH.sub.3 H white 195-197 32.8 2.75 17.7 6.73 powder (d) 33.1 2.67 17.4 6.7840 CH.sub.3 H OCH.sub.3 Br CH.sub.3 H tan powder 187-190 36.4 3.05 19.6 7.47 (d) 36.7 3.18 19.4 7.8341 CH.sub.3 F H Br CH.sub.3 H white 180-182 34.6 2.42 20.1 7.68 powder (d) 34.7 2.57 20.1 7.8242 CH.sub.3 CH.sub.3 H Br CH.sub.3 H white 183-185 37.8 3.17 20.3 7.76 powder (d) 38.0 3.56 19.9 8.0543 CH.sub.3 H OCH.sub.3 SC.sub.2 H.sub.5 CH.sub.3 H light yellow 176-178 43.9 4.42 20.5 15.6 powder (d) 43.7 4.51 20.0 14.944 CH.sub.3 F H SC.sub.2 H.sub.5 CH.sub.3 H light gray 170-172 42.2 3.79 21.1 16.1 powder (d) 42.5 3.94 20.9 15.845 CH.sub.3 F H F CH.sub.3 H white 190-192 40.5 2.83 23.6 9.00 powder 40.5 2.53 23.5 9.0946 CH.sub.3 OCH.sub.3 H F CH.sub.3 H white 204-205 42.4 3.56 22.8 8.70 powder (d) 42.3 3.67 22.6 8.9447 CH.sub.3 Cl H Cl OCH.sub.3 H white 183-185 35.6 2.49 20.7 7.91 powder (d) 35.6 2.31 20.4 7.9248 CH.sub.3 H Cl Cl CH.sub.3 H white 194-195 35.6 2.49 20.7 7.91 powder (d) 35.7 2.38 20.5 7.8949 C.sub.2 H.sub.5 Cl H Cl CH.sub.3 H tan powder 188-189 38.7 3.00 20.8 7.95 (d) 38.8 2.93 20.7 7.9450 C.sub.2 H.sub.5 Cl H F CH.sub.3 H tan powder 195-196 40.4 3.13 21.7 8.29 (d) 40.5 3.04 21.7 8.5351 C.sub.2 H.sub.5 CH.sub.3 H Cl OCH.sub.3 H white solid 194-195 42.2 3.79 21.1 8.04 42.4 4.02 19.9 8.0352 CH.sub.3 H Br F CH.sub.3 H tan powder 189-191 34.6 2.42 20.1 7.68 (d) 34.9 2.83 19.9 7.9653 C.sub.2 H.sub.5 CH.sub.3 H F CH.sub.3 H white 210-211 45.9 4.13 22.9 8.75 powder (d) 46.1 4.17 23.1 8.9454 C.sub.2 H.sub.5 H F F CH.sub.3 H white 204-205 42.2 3.27 22.7 8.66 powder (d) 42.2 2.87 22.4 8.7755 C.sub.2 H.sub.5 H F Cl CH.sub.3 H white 216-217 40.4 3.13 21.7 8.29 powder (d) 40.5 2.97 21.7 8.1156 C.sub.2 H.sub.5 H F Cl OCH.sub.3 H white 205-207 38.8 3.00 20.9 7.96 powder (d) 39.0 2.96 20.8 8.0657 CH.sub.3 F H Cl OCH.sub.3 H white 187-189 37.1 2.59 21.6 8.25 powder (d) 37.3 2.46 21.5 8.2258 CH.sub.3 OCH.sub.3 H Cl OCH.sub.3 H tan 197-199 39.0 3.27 21.0 solid (d) 38.9 3.40 20.959 CH.sub.3 H CH.sub.3 Cl OCH.sub.3 H tan 197-198 40.6 3.41 21.8 solid (d) 40.4 3.42 21.160 CH.sub.3 CH.sub.2 -- H F CH.sub.3 H white 199-200 44.0 3.95 22.0 8.38 OCH.sub.3 powder (d) 43.9 3.92 21.8 8.5061 CH.sub.3 H F Cl OCH.sub.3 H white 185-190 37.1 2.59 21.6 8.25 powder (d) 37.1 2.38 21.4 8.2562 CH.sub.3 SCH.sub.3 H Cl OCH.sub.3 H white 185-186 37.5 3.14 20.2 15.4 powder (d) 37.5 3.26 20.2 15.263 C.sub.2 H.sub.5 Cl H Cl OCH.sub.3 H white 183-184 37.2 2.89 20.0 7.65 powder (d) 37.5 2.72 19.8 7.8864 CH.sub.3 F H F H CH.sub.3 white 178-179 40.5 2.83 23.6 9.00 powder (d) 40.3 2.93 23.4 9.2565 CH.sub.3 CH.sub.3 H F CH.sub.3 H white 191-192 44.3 3.72 23.9 9.10 powder (d) 44.2 3.82 23.9 9.3666 CH.sub.3 H OCH.sub.3 F H CH.sub.3 white solid 174-176 (d)67 CH.sub.3 H OCH.sub.3 H CF.sub.3 H light yellow 221-222 38.6 2.74 20.8 7.93 solid 38.5 2.63 20.5 7.7668 CH.sub.3 CH.sub.3 H H CF.sub.3 H white 193-194 40.2 2.86 21.6 8.26 powder 40.0 2.66 21.7 8.4369 CH.sub.3 CH.sub.3 H H CO.sub.2 CH.sub.3 H white 156-157 44.4 3.73 22.2 8.47 powder 44.6 3.59 22.1 8.5870 C.sub.2 H.sub.5 F H F H Cl tan powder 193-194 36.9 2.32 21.5 8.20 (d) 37.1 2.43 21.4 7.9871 CH.sub.3 CH.sub.3 H F H Cl white 205-206 38.7 2.70 22.6 8.60 powder (d) 38.5 2.57 22.5 8.6072 C.sub.2 H.sub.4 Cl CH.sub.3 H F CH.sub.3 H tan powder 180-18473 CH.sub.2 CF.sub.3 CH.sub.3 H F CH.sub.3 H white 215-218 40.0 2.88 20.0 7.63 powder 40.1 2.66 19.8 7.4574 CH.sub.3 CH.sub.3 H H CH.sub.3 H white solid 188-190 46.7 4.22 25.1 9.59 46.8 4.06 24.9 9.8775 C.sub.2 H.sub.5 CH.sub.3 H H CO.sub.2 CH.sub.3 H white 180-181 45.9 4.11 21.4 8.17 powder 46.2 4.01 21.6 8.3476 C.sub.2 H.sub.5 F H H CH.sub.3 H white 161-163 44.3 3.72 23.9 9.10 powder 44.4 4.09 23.6 8.9377 CH.sub.3 F OCH.sub.3 F CH.sub.3 H tan 177-180 40.4 3.13 21.8 8.30 solid 40.7 3.61 21.1 8.0578 CH.sub.3 CH.sub.3 H OCH.sub.3 CH.sub.3 H white solid 215-216 46.2 4.43 23.1 8.80 46.3 4.56 23.2 8.3679 CH.sub.3 CH.sub.3 H H CO.sub.2 C.sub.2 H.sub.5 H white solid 152-153 45.9 4.12 21.4 8.17 45.5 4.24 21.5 8.1280 CH.sub.3 CH.sub.3 H Cl Cl H white solid 195-196 37.0 2.59 21.6 8.24 (d) 40.8 3.13 21.8 7.7681 CH.sub.3 CH.sub.3 H Cl OC.sub.2 H.sub.5 H white solid 202-203 42.2 3.79 21.1 8.04 42.4 3.38 21.1 7.7282 CH.sub.3 F H Cl OC.sub.2 H.sub.5 H white solid 156-157 40.3 3.39 20.2 7.69 40.4 3.65 20.0 7.7883 CH.sub.3 CH.sub.3 H H CO.sub.2 -- H white solid 158-159 47.3 4.46 20.7 7.89 C.sub.3 H.sub.7 (i) 47.5 4.84 20.7 7.4684 CH.sub.3 CH.sub.3 H H OC.sub.2 H.sub.5 H white solid 184-186 46.2 4.43 23.1 8.08 46.5 4.37 22.8 7.9885 C.sub.2 H.sub.5 F H H CO.sub.2 -- H white solid 168-169 45.3 4.04 19.8 7.55 C.sub.3 H.sub.7 (i) 45.5 4.20 19.6 7.4886 CH.sub.3 CH.sub.3 H H Cl H white solid 218-223 47.3 3.64 20.3 7.73 (d) 47.5 3.50 20.1 7.4387 CH.sub.3 H OCH.sub.3 F C.sub.2 H.sub.5 H white solid 191-192 44.0 3.95 22.0 8.38 (d) 43.8 3.73 22.0 8.5788 C.sub.2 H.sub.5 F H F C.sub.2 H.sub.5 H white solid 192-193 43.8 3.67 21.9 8.34 (d) 43.8 3.57 21.8 8.5789 CH.sub.3 CH.sub.3 H F C.sub.2 H.sub.5 H white solid 208-209 45.9 4.13 22.9 8.76 45.7 4.40 22.8 8.7690 CH.sub.3 CH.sub.3 H Cl OC.sub.3 H.sub.7 (n) H white solid 175-176 43.6 4.15 20.3 7.77 44.0 4.20 20.4 7.4591 CH.sub.3 CH.sub.3 H Cl OC.sub.3 H.sub.7 (i) H white solid 199-200 43.6 4.15 20.4 7.77 43.5 4.11 20.5 7.3992 C.sub.2 H.sub.5 F H Cl OC.sub.3 H.sub.7 (n) H tan solid 159-160 41.8 3.74 19.5 7.44 (d) 41.9 3.83 19.4 7.7293 C.sub.2 H.sub.5 F H Cl OC.sub.3 H.sub.7 (i) H white solid 181-182 41.8 3.74 19.5 7.44 (d) 41.6 3.96 18.9 7.5894 CH.sub.3 CH.sub.3 H F C.sub.3 H.sub.7 (i) H white solid 199-200 47.4 4.50 22.1 8.43 (d) 47.4 4.61 21.9 8.3295 CH.sub.3 F H Cl OC.sub.3 H.sub.7 (i) H white solid 109-211 40.3 3.39 20.2 7.69 (d) 39.9 3.57 19.9 7.4296 C.sub.2 H.sub.5 CH.sub.3 H F OC.sub.3 H.sub.7 (i) H white solid 212-213 45.0 4.49 19.7 7.51 (d) 44.9 4.40 19.5 6.6597 C.sub.2 H.sub.5 F H Cl Cl Cl white solid 218-219 32.6 1.83 19.0 7.26 (d) 33.0 1.96 19.1 7.1498 CH.sub.3 CH.sub.3 H Cl Cl Cl white solid 200-202 34.0 2.14 19.8 7.57 (d) 34.3 1.91 19.7 7.4399 CH.sub.3 H Br Cl OC.sub.2 H.sub.5 H white solid 174-175 33.7 2.61 18.1 6.91 (d) 33.8 2.67 17.9 7.03100 CH.sub.3 H Br Cl OCH.sub.3 H white solid 194-197 32.1 2.24 18.7 7.13 (d) 32.2 2.30 18.8 7.00101 C.sub.2 H.sub.5 CH.sub.3 H Cl OC.sub.2 H.sub.5 H white solid 196-198 43.6 4.15 20.4 7.77 (d) 43.6 4.26 20.2 7.92102 CH.sub.3 H I Cl OC.sub.2 H.sub.5 H tan solid 184-185 30.6 2.37 16.5 6.28 (d) 30.7 2.39 16.0 5.46103 CH.sub.3 H Cl Cl OC.sub.2 H.sub.5 H yellow solid 172-173 37.2 2.89 20.1 7.65 (d) 37.4 3.06 19.7 7.01104 C.sub.2 H.sub.5 CH.sub.3 H Cl OC.sub.3 H.sub.7 (n) H yellow solid 165-167 45.0 4.49 19.7 7.51 (d) 44.9 4.51 19.3 7.21105 CH.sub.3 CH.sub.3 H Cl CO.sub.2 CH.sub.3 H white solid 206-208 40.7 3.17 20.4 7.77 (d) 40.6 3.05 20.2 7.69106 CH.sub.3 C.sub.3 H.sub.7 (i) H F CH.sub.3 H orange solid 160-162 47.4 4.50 22.1 8.43 47.9 4.26 20.1 7.56107 C.sub.3 H.sub.7 (i) CH.sub.3 H Cl OCH.sub.3 H colorless 202-203 43.6 4.15 20.4 7.77 solid (d) 43.4 4.18 20.1 7.58108 C.sub.3 H.sub.7 (i) CH.sub.3 H F CH.sub.3 H tan solid 198-199 47.4 4.50 22.1 8.43 (d) 47.4 4.39 21.4 7.67109 C.sub.3 H.sub.7 (i) CH.sub.3 H Cl OC.sub.2 H.sub.5 H yellow solid 168-170 45.0 4.29 19.7 7.51 45.2 4.79 19.4 7.40110 CH.sub.3 CH.sub.3 H H CO.sub.2 CH.sub.3 H white solid 218-222 43.8 4.14 19.1 7.37 (acetic acid (d) 44.0 4.20 20.0 7.05 adduct)111 CH.sub.3 Cl H Cl OC.sub.2 H.sub.5 H white solid 198-199 37.2 2.89 20.1 7.65 (d) 37.0 2.85 -- 7.32112 C.sub.2 H.sub.5 Cl H Cl OC.sub.2 H.sub.5 H tan solid 177-179 38.8 3.26 19.4 7.40 (d) 38.9 3.48 19.1 7.64113 CH.sub.3 CF.sub.3 H Cl OCH.sub.3 H lt. tan solid 181-183 35.6 2.30 19.2 7.31 (d) 35.8 2.53 18.8 6.82114 CH.sub.3 CF.sub.3 H F CH.sub.3 H lt. tan solid 165-166 38.2 2.47 20.6 7.85 (d) 38.1 2.51 20.2 7.62115 C.sub.3 H.sub.7 (n) CH.sub.3 H Cl OC.sub.2 H.sub.5 H lt. yellow 187-188 45.0 4.49 19.7 7.51 solid 45.0 4.68 19.7 7.38116 C.sub.3 H.sub.7 (n) CH.sub.3 H Cl OC.sub.3 H.sub.7 (n) H white solid 181-182 46.3 4.80 19.1 7.27 46.4 5.04 19.0 7.06117 C.sub.3 H.sub.7 (n) CH.sub.3 H Cl OCH.sub.3 H white 209-210 43.6 4.15 20.4 7.77 solid (d) 43.5 4.25 20.2 7.45118 C.sub.2 H.sub.5 CH.sub.3 H Cl CO.sub.2 CH.sub.3 H white solid 209-210 42.2 3.54 19.7 7.51 42.1 3.77 19.5 7.24119 CH.sub.3 CH.sub.3 H Br OCH.sub.3 H white solid 169-170 36.4 3.05 19.6 7.47 36.0 3.34 18.5 6.49120 C.sub.2 H.sub.5 CH.sub.3 H Br OCH.sub.3 H tan solid 191-192 37.9 3.41 19.0 7.23 (d) 38.0 3.40 18.4 7.00121 CH.sub.3 CH.sub.3 H Cl OCH.sub.2 CF.sub.3 H white solid 199-200 37.1 2.67 18.6 7.08 (d) 37.3 2.80 18.5 6.93122 C.sub.2 H.sub.5 CH.sub.3 H Cl OCH.sub.2 CF.sub.3 H white solid 200-201 38.6 3.02 18.0 6.87 (d) 38.8 3.07 18.0 6.64123 C.sub.2 H.sub.5 CH.sub.3 H F OCH.sub.3 H white solid 201-202 44.0 3.95 22.0 8.38 (d) 43.9 3.88 21.7 8.03124 CH.sub.3 CH.sub.3 H F OCH.sub.3 H white solid 197-198 40.1 3.91 21.8 8.30 (d) 40.3 4.02 21.7 8.04125 CH.sub.3 F CH.sub.3 F CH.sub.3 H lt. brown 171-172 42.2 3.27 22.7 8.66 solid (d) 42.0 3.57 21.5 8.07126 CH.sub.3 F CH.sub.3 Cl OCH.sub.3 H tan solid 219-221 38.8 3.00 20.9 7.96 39.0 2.69 20.9 7.77127 CH.sub.3 CH.sub.3 H F OC.sub.2 H.sub.5 H white solid 194-195 44.0 3.95 22.0 8.38 (d) 43.7 3.99 22.0 8.03128 C.sub.2 H.sub.5 CH.sub.3 H F OC.sub.2 H.sub.5 H white solid 203-204 45.5 4.32 21.2 8.09 45.2 4.03 21.0 7.76129 CH.sub.3 CH.sub.3 H Br OC.sub.2 H.sub.5 H tan solid 182-184 37.9 3.41 19.0 7.23 38.0 3.60 18.9 7.09130 CH.sub.3 CH.sub.3 H Br OC.sub.3 H.sub.7 (n) H white solid 153-155 39.4 3.75 18.4 7.01 39.3 3.94 18.3 6.61131 C.sub.2 H.sub.5 CH.sub.3 H Br OC.sub.2 H.sub.5 H pink solid 194-195.5 39.4 3.75 18.4 7.01 39.0 3.88 18.3 6.79132 C.sub.2 H.sub.5 CH.sub.3 H Br OC.sub.3 H.sub.7 (n) H white solid 181-183 40.8 4.06 17.8 6.80 40.8 4.24 17.9 6.54133 CH.sub.3 CH.sub.3 H Br OC.sub.3 H.sub.7 (i) H white solid 182-184 39.4 3.75 18.4 7.01 38.8 3.83 18.1 6.62134 C.sub.2 H.sub.5 CH.sub.3 H Br OC.sub.3 H.sub.7 (i) H white solid 197-198 40.8 4.06 17.8 6.80 40.4 4.21 17.7 6.39135 CH.sub.3 CH.sub.3 H Cl OC.sub.4 H.sub.9 (n) H white solid 109-111 45.1 4.49 19.7 7.51 45.2 4.57 19.8 7.08136 CH.sub.3 CH.sub.3 H Cl OC.sub.4 H.sub.9 (i) H white solid 160-192 45.1 4.49 19.7 7.51 45.2 4.68 19.9 7.34137 CH.sub.3 CH.sub.3 H OCH.sub.3 Cl H white solid 218-222 40.6 3.41 21.8 8.33 (d) 40.4 3.37 21.9 --138 C.sub.2 H.sub.5 CH.sub.3 H Cl OC.sub.4 H.sub.9 (i) H yellow solid 139-141 46.3 4.80 19.1 7.27 45.1 4.99 18.3 6.78139 C.sub.2 H.sub.5 CH.sub.3 H Cl OC.sub.4 H.sub.9 (s) H white solid 188-189 46.3 4.80 19.1 7.27 46.3 4.93 19.3 7.16140 C.sub.2 H.sub.5 CH.sub.3 H Cl OC.sub.4 H.sub.9 (n) H white solid 98-100 46.3 4.80 19.1 7.27 46.4 5.05 18.9 6.77141 C.sub.2 H.sub.5 CH.sub.3 H OCH.sub.3 Cl H white solid 233-234 42.2 3.79 21.1 8.04 41.7 3.70 20.8 7.99142 CH.sub.3 CH.sub.3 H Cl OC.sub.2 H.sub.4 F H off-white 189-109 40.3 3.39 20.2 7.69 solid (d) 40.0 3.40 19.5 7.92143 C.sub.2 H.sub.5 CH.sub.3 H Cl OC.sub.2 H.sub.4 F H off-white 209-210 41.8 3.74 19.5 7.44 solid 41.6 3.66 19.0 6.11144 CH.sub.3 CH.sub.3 H Cl OC.sub.4 H.sub.9 (s) H tan solid 162.5-164 45.0 4.49 19.7 7.51 45.2 4.53 19.4 7.65145 CH.sub.3 CH.sub.3 H F I H white 207-208 31.1 2.17 18.1 6.91 solid (d) 31.2 2.09 18.3 6.61146 C.sub.2 H.sub.5 CH.sub.3 H F I H white 208-209 32.7 2.53 17.6 6.70 solid (d) 33.0 2.40 17.6 6.41147 CH.sub.3 CH.sub.3 H OCH.sub.3 CO.sub.2 CH.sub.3 H white 206-207 44.1 3.95 20.6 7.85 solid (d) 43.8 3.61 20.6 7.43148 C.sub.2 H.sub.5 CH.sub.3 H OCH.sub.3 CO.sub.2 CH.sub.3 H white 208-209 45.5 4.30 19.9 7.59 solid (d) 45.2 4.91 19.7 7.20149 CH.sub.3 CH.sub.3 H F OC.sub.3 H.sub.7 (i) H white 198-199 45.5 4.32 21.2 8.09 solid (d) 45.2 5.07 21.5 7.84150 C.sub.2 H.sub.5 CH.sub.3 H F OC.sub.3 H.sub.7 (i) H off-white 214-215 46.8 4.67 20.5 7.81 solid (d) 46.5 4.94 20.5 7.37151 CH.sub.3 CH.sub.3 H F OC.sub.3 H.sub.7 (n) H yellow 176-177 45.5 4.32 21.7 8.09 solid 45.1 4.56 21.1 7.70152 C.sub.2 H.sub.5 CH.sub.3 H F OC.sub.3 H.sub.7 (n) H white 195-196 46.8 4.67 20.5 4.81 solid 46.4 4.57 20.5 4.47153 CH.sub.3 CH.sub.3 H F CO.sub.2 CH.sub.3 H tan 170-171 42.4 3.31 21.2 8.09 solid (d) 42.3 3.56 20.9 7.48154 C.sub.2 H.sub.5 CH.sub.3 H F CO.sub.2 CH.sub.3 H white 162-164 43.9 3.68 20.5 7.81 solid (d) 43.9 4.23 19.7 7.16155 CH.sub.3 CH.sub.3 H OCH.sub.3 CF.sub.3 H white 204-205 40.2 3.13 20.1 7.66 solid 40.2 3.01 20.4 7.54156 C.sub.2 H.sub.5 CH.sub.3 H OCH.sub.3 CF.sub.3 H tan 209-211 41.7 3.50 19.4 7.41 solid 41.7 3.40 19.5 7.19157 C.sub.2 H.sub.5 CH.sub.3 H Cl OC.sub.2 H.sub.4 -- H white 138-140 43.4 4.32 19.0 7.24 OCH.sub.3 solid (d) 43.4 4.52 19.1 6.78158 CH.sub.3 CH.sub.3 H Cl OC.sub.2 H.sub.4 -- H white 166-168 42.0 4.00 19.6 7.48 OCH.sub.3 solid (d) 40.9 4.30 18.9 6.74159 CH.sub.3 CH.sub.3 H Cl OC.sub.2 H.sub.4 Cl H white 187-188 38.8 3.26 19.4 7.40 solid (d) 39.1 3.57 19.5 6.84160 C.sub.2 H.sub.5 CH.sub.3 H Cl OC.sub.2 H.sub.4 Cl H white 196.5-198 40.3 3.61 18.4 7.17 solid 39.9 2.50 18.7 7.65161 C.sub.2 H.sub.5 CH.sub.3 H Cl OCH.sub.2 CHF.sub.2 H white 195-196 40.1 3.37 18.7 7.14 solid (d) 40.0 3.53 18.7 6.78162 CH.sub.3 CH.sub.3 H Cl OCH.sub.2 CHF.sub.2 H white 174-175 38.7 3.01 19.3 7.38 solid (d) 38.2 3.28 19.1 7.02163 CH.sub.3 CH.sub.3 H Cl OCH.sub.3 (CH.sub.3)-- H white 198.5-200 38.6 3.02 18.0 6.87 CF.sub.3 solid 38.5 3.38 17.8 6.39164 C.sub.2 H.sub.5 CH.sub.3 H Cl OCH(CH.sub.3)-- H white solid 224-225.5 40.0 3.35 17.5 6.67 CF.sub.3 40.0 3.62 17.3 6.39165 C.sub.2 H.sub.5 CH.sub.3 H OCH.sub.3 F H white solid 221-222 44.1 3.70 22.0 43.7 3.72 21.4166 CH.sub.3 CH.sub.3 H OCH.sub.3 CO.sub.2 C.sub.2 H.sub.5 H white solid 198-199 45.5 4.30 19.9 7.59 (d) 45.2 4.20 20.1 7.31167 C.sub.2 H.sub.5 CH.sub.3 H OCH.sub.3 CO.sub.2 C.sub.2 H.sub.5 H white solid 200-201 46.8 4.62 19.3 7.35 46.6 4.51 19.4 7.10168 CH.sub.3 CH.sub.3 H OC.sub.2 H.sub.5 CO.sub.2 CH.sub.3 H lt. gray 178-179 45.5 4.30 19.9 7.59 solid (d) 45.8 4.49 20.1 7.34169 C.sub.2 H.sub.5 CH.sub.3 H OC.sub.2 H.sub.5 CO.sub.2 CH.sub.3 H white solid 192-194 46.8 4.62 19.3 7.35 (d) 46.8 4.57 19.5 7.17170 CH.sub.3 CH.sub.3 H OCH.sub.3 F H white solid 215-216 42.4 3.56 22.8 8.70 (d) 42.1 3.54 22.5 8.54171 CH.sub.3 CH.sub.3 H OC.sub.2 H.sub.5 Cl H off-white 180-182 42.2 3.79 21.1 8.04 solid (d) 42.2 3.72 20.9 7.77172 C.sub.2 H.sub.5 CH.sub.3 H OC.sub.2 H.sub.5 Cl H off-white 199-201 43.6 4.15 20.4 7.77 solid (d) 43.5 4.17 20.3 7.75173 CH.sub.3 CH.sub.3 H OCH.sub.3 SCH.sub.3 H light yellow 219-220 42.4 4.07 21.2 solid (d) 41.4 4.19 20.0174 C.sub.2 H.sub.5 CH.sub.3 H OCH.sub.3 SCH.sub.3 H white solid 241-242 43.9 4.42 20.5 (d) 43.4 4.13 19.5175 CH.sub.3 CH.sub.3 H F SCH.sub.3 H light yellow 206-207 40.6 3.41 21.9 16.7 solid (d) 40.6 3.46 20.8 16.4176 C.sub.2 H.sub.5 CH.sub.3 H F SCH.sub.3 H white solid 218-219 42.2 3.79 21.1 16.1 (d) 41.9 3.59 20.9 16.1177 CH.sub.3 CH.sub.3 H CH.sub.3 CO.sub.2 CH.sub.3 H178 C.sub.2 H.sub.5 CH.sub.3 H CH.sub.3 CO.sub.2 CH.sub.3 H__________________________________________________________________________
The compounds of Formula I wherein V represents hydrogen can generally be prepared by combining a 2-chlorosulfonyl[1,2,4]triazolo[1,5-c]pyridine compound of Formula II: ##STR4## with an appropriately substituted aminopyridine compound of Formula III: ##STR5## in the presence of pyridine or a methylpyridine compound, and, optionally but preferably, a catalytic amount of dimethyl sulfoxide. The substituents OR, Y, and Z of Formula II and A, B, and D of Formulas III are as defined hereinbefore.
The preparation is usually accomplished by combining the 2-chlorosulfonyl[1,2,4]triazolo[1,5-c]pyrimidine compound Formula II, the aminopyridine of Formula III, and an inert solvent, such as acetonitrile, N,N-dimethylformamide, N-methyl-2-pyrrolidinone, tetrahydrofuran, and the like, in a vessel and then adding the pyridine or methylpyridine, preferably pyridine, and a catalytic amount of dimethyl sulfoxide. The mixture is allowed to react, typically at ambient temperature, but with heating, if necessary. After a substantial quantity of the compound of Formula I has formed or a substantial quantity of the chlorosulfonyl compound of Formula II has been consumed, the desired product is recovered, typically removing the solvent by evaporation, adding water, and removing the liquids from the solid that forms by filtration or centrifugation. The product recovered can be purified, if desired, by extracting with an immiscible organic solvent, such as methylene chloride, and with water. Alternatively, the desired compounds of Formula I can be purified by recrystallization and by other commonly used methods.
Approximately equimolar quantities of the compounds of Formulas II and III are generally used in the preparation of compounds of Formula I although a substantial excess of one or the other may be employed. The pyridine or methylpyridine compound is generally employed in an amount of from at least 1 to about 5 moles per mole of compound of Formula II. Dimethyl sulfoxide is typically used in less than an equimolar amount; amounts over about 0.3 mole per mole of compound of Formula II are usually deleterious. Acetonitrile is often the preferred solvent.
It is sometimes advantageous to prepare the compounds of Formula I by condensing a chlorosulfonyl compound of Formula II with an N-trialkylsilyl derivative of a substituted aminopyridine compound. The method employed is analogous to that described in U.S. Pat. No. 4,910,306 for N-trialkylsilylanilines. The reaction conditions required are essentially the same as those described hereinabove for the condensation of a compound of Formula II with a substituted aminopyridine with the exception that the pyridine compound base may be omitted. The substituted N-trialkylsilylaminopyridine compounds employed can be prepared from the corresponding substituted aminopyridine compounds by treatment with a trialkylsilyl halide and a trialkylamine as described in U.S. Pat. No. 4,910,306 for aniline compounds. Sodium iodide is typically employed as a catalyst when the halide is chloride. The N-trialkylsilylaminopyridine compounds are typically prepared and used immediately and without purification.
Compounds of Formula I wherein V represents hydrogen and OR represents (C.sub.1 -C.sub.3)alkoxy optionally monosubstituted with chloro or methoxy or 2,2,2-trifluoroethoxy can be made from the corresponding compounds related to those of Formula I wherein the moiety OR in the 5-position is replaced by chloro by treatment with an appropriate alkoxide reagent, such as sodium methoxide in methanol. The reaction conditions employed are similar to those used for the related exchange reactions of 2- and 4-chloropyrimidines. Non-aqueous media are preferred. Selective replacement of chlorine in the 5-position can readily be achieved as this chlorine is much more reactive than chlorine in the 7-and 8-positions (Y and/or Z represent Cl).
Compounds of Formula I wherein V represents COR', CO.sub.2 R", or CONR"'.sub.2 can be prepared from compounds of Formula I wherein V represents hydrogen by acylation with a compound of the formula C.sub.1 COR', C.sub.1 CO.sub.2 R", or C.sub.1 CONR"'.sub.2, respectively, using conventional procedures known in the art for the acylation of sulfonamides.
The 2-chlorosulfonyl[1,2,4]triazolo[1,5-c]pyrimidine compounds of Formula II and their analogs wherein the moiety OR is replaced by chloro can be prepared by the methods taught in U.S. Pat. No. 5,010,195.
The preparation of several substituted 3-aminopyridines, notably those wherein A represents chloro or fluoro, and B represents alkyl, alkoxy or alkylthio is described in the Examples. Other substituted 3-aminopyridines of interest as intermediates for the compounds of Formula I are known in the art or can be prepared by the general methods known in the art or provided herein.
4-Alkoxy-3-amino-2-chloropyridine compounds can be prepared by chlorination of known 4-alkoxy-3-aminopyridine compounds. 4-Alkoxy-3-amino-2-fluoropyridine compounds can be prepared from 4-alkoxy-2-fluoropyridine compounds by lithiation with butyl lithium and treatment of the intermediate with diphenyl phosphoryl azide. 4-Alkoxy-2-fluoropyridine compounds can be prepared by reduction of 4-Alkoxy-3,5-dichloro-2-fluoropyridine. compounds with hydrogen. Many 4-substituted 2-alkoxy-3-aminopyridine compounds can be prepared from 2-alkoxy-3-aminopyridine compounds by lithiation of the corresponding t-butoxycarbonyl derivative and reaction of this with an electrophilic reagent in processes closely related to those disclosed in J. Organic Chemistry, 60, 1875-1877 (1995). Thus, 2-alkoxy-3-amino-4-fluoropyridine compounds can be prepared from [-butyl N-(2-alkoxy-3-pyridinyl)carbamates by fluorination with N-fluorodibenzenesulfonimide of the intermediate obtained on lithiation with t-butyl lithium followed by treatment with anhydrous p-toluenesulfonic acid to remove the protecting t-butoxycarbonyl group. Similarly, 2-alkoxy-3-amino-4-chloropyridine compounds can be obtained by chlorination of t-butyl N-(2-alkoxy-3-pyridinyl)carbamates with hexachloroethane in an analogous process. Alkyl 3-amino-2-alkoxyisonicotinate compounds can be prepared analogously from t-butyl N-(2-alkoxy-3-pyridinyl)carbamate compounds by lithiating with butyl lithium, treating the intermediate formed with carbon dioxide and then an alkyl iodide, and finally removing the protecting t-butoxycarbonyl group by treatment with anhydrous p-toluenesulfonic acid. The amine-protected t-butyl N-(2-alkoxy-3-pyridinyl)carbamate compounds can be prepared from 2-alkoxy-3-aminopyridine compounds by treatment with di-t-butyl dicarbonate. 3-Amino-2-chloroisonicotinic acid esters can be prepared by chlorination of 3-aminoisonicotinic acid esters using 1,3-dichloro-5,5-dimethylhydantion as the chlorinating agent. 3-Amino-2-fluoro-4-methylpyridine can be prepared by palladium on carbon catalyzed reduction of 2-fluoro-4-methyl-3-nitropyridine with hydrogen. This compound can be converted to other 4-alkyl-3-amino-2-fluoropyridine compounds by alkylation of the methyl group. These and other 3-aminopyridine compounds of Formula III can be made using a variety of preparative methods well-established in the art.
while it is possible to utilize the [1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide compounds of Formula I directly as herbicides, it is preferable to use them in mixtures containing an herbicidally effective amount of the compound along with at least one agriculturally acceptable adjuvant or carrier. Suitable adjuvants or carriers should not be phytotoxic to valuable crops, particularly at the concentrations employed in applying the compositions for selective weed control in the presence of crops, and should not react chemically with the compounds of Formula I or other composition ingredients. Such mixtures can be designed for application directly to weeds or their locus or can be concentrates or formulations which are normally diluted with additional carriers and adjuvants before application. They can be solids, such as, for example, dusts, granules, water dispersible granules, or wettable powders, or liquids, such as, for example, emulsifiable concentrates, solutions, emulsions or suspensions.
Suitable agricultural adjuvants and carriers that are useful in preparing the herbicidal mixtures of the invention are well known to those skilled in the art.
Liquid carriers that can be employed include water, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol monomethyl ether and diethylene glycol monomethyl ether, methanol, ethanol, isopropanol, amyl alcohol, ethylene glycol, propylene glycol, glycerine, and the like. Water is generally the carrier of choice for the dilution of concentrates.
Suitable solid carriers include talc, pyrophyllite clay, silica, attapulgus clay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonire clay, Fuller's earth, cotton seed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour, lignin, and the like.
It is frequently desirable to incorporate one or more surface-active agents into the compositions of the present invention. Such surface-active agents are advantageously employed in both solid and liquid compositions, especially those designed to be diluted with carrier before application. The surface-active agents can be anionic, cationic or nonionic in character and can be employed as emulsifying agents, wetting agents, suspending agents, or for other purposes. Typical surface active agents include salts of alkyl sulfates, such as diethanoiammonium lauryl sulfate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-C.sub.18 ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol-C.sub.16 ethoxylate; soaps, such as sodium stearate; alkylnaphthalenesulfonate salts, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2-ethylhexyl) sulfosucclinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono and dialkyl phosphate esters.
Other adjuvants commonly utilized in agricultural compositions include antifoam agents, compatibilizing agents, sequestering agents, neutralizing agents and buffers, corrosion inhibitors, dyes, odorants, penetration aids, spreading agents, sticking agents, dispersing agents, thickening agents, freeze point depressants, antimicrobial agents, and the like. The compositions can also contain other compatible components, for example, other herbicides, plant growth regulants, fungicides, insecticides, and the like and can be formulated with liquid fertilizers or solid, particulate fertilizer carriers such as ammonium nitrate, urea and the like.
The concentration of the active ingredients in the herbicidal compositions of this invention is generally from about 0.001 to about 98 percent by weight. Concentrations from about 0.01 to about 90 percent by weight are often employed. In compositions designed to be employed as concentrates, the active ingredient is generally present in a concentration from about 5 to about 98 weight percent, preferably about 10 to about 90 weight percent. Such compositions are typically diluted with an inert carrier, such as water, before application. The diluted compositions usually applied to weeds or the locus of weeds generally contain about 0.001 to about 5 weight percent active ingredient and preferably contain about 0.01 to about 0.5 percent.
The present compositions can be applied to weeds or their locus by the use of conventional ground or aerial dusters, sprayers, and granule applicators, by addition to irrigation water, and by other conventional means known to those skilled in the art.
The compounds of Formula I have been found to be useful preemergence and postemergence herbicides. They can be employed at non-selective (higher) rates of application to control essentially all of the vegetation in an area or, in some cases, at selective (lower) rates of application for the selective control of undesirable vegetation in grass crops, such as corn, wheat, barley, and rice as well as in broadleaf crops, such as soybeans and cotton. While each of the N-pyridinyl[1,2,4]triazolo[1,5-a]pyrimidine-2-sulfonamide compounds encompassed by Formula I is within the scope of the invention, the degree of herbicidal activity, the crop selectivity, and the spectrum of weed control obtained varies depending upon the substituents present.
The term herbicide is used herein to mean an active ingredient which controls or adversely modifies the growth of plants. An herbicidally effective or vegetation controlling amount is an amount of active ingredient which causes an adversely modifying effect and includes deviations from natural development, killing, regulation, desiccation, retardation, and the like. The terms plants and vegetation are meant to include germinant seeds, emerging seedlings and established vegetation.
Herbicidal activity is exhibited by the compounds of the present invention when they are applied directly to the plant or to the locus of the plant at any stage of growth or before emergence. The effect observed depends upon the plant species to be controlled, the stage of growth of the plant, the application parameters of dilution and spray drop size, the particle size of solid components, the environmental conditions at the time of use, the specific compound employed, the specific adjuvants and carriers employed, the soil type, and the like, as well as the amount of chemical applied. These and other factors can be adjusted as is known in the art to promote selective herbicidal action. Generally, it is preferred to apply the compounds of Formula I postemergence to relatively immature plants to achieve the maximum control of broadleaf weeds.
Application rates of about 0.001 to about 1 Kg/Ha are generally employed in postemergence operations; for preemergence applications, rates of about 0.01 to about 10 Kg/Ha are generally employed. The higher rates designated generally give non-selective control of a broad variety of undesirable vegetation. The lower rates typically give selective control and, by judicious election, can be employed in the locus of crops.
EXAMPLES
The following Examples are presented to illustrate the various aspects of this invention and should not be construed as limitations to the claims.
1. Preparation of 3-Amino-2-fluoro-4-methylpyridine
To a solution of 10.1 g (grams) (65 mmol (millimole)) of 2-fluoro-4-methyl-3-nitropyridine in 200 mL (milliliter) of ethyl acetate was added 25 g (0.40 mol) of acetic acid and 0.8 g of 5 percent palladium on carbon catalyst. This mixture was shaken under 50 psig (pounds per square inch gauge, 2400 kiloPascals) pressure of hydrogen for 18 hours, was filtered, and was concentrated by evaporation under reduced pressure to obtain an oil. This oil was partitioned between dilute aqueous sodium bicarbonate and ether. The organic phase was separated, dried over magnesium sulfate, and filtered. The filtrate was concentrated by evaporation under reduced pressure and the residue was purified by column chromatography to obtain 7.2 g (88 percent of theory) of the title compound as a colorless solid melting at 63.degree.-64.degree. C.
Elemental Analysis C.sub.6 H.sub.7 FN.sub.2 Calc.: %C, 57.1; %H, 5.59; %N, 22.2 Found: %C, 57.2; %H, 5.73; %N, 22.1
.sup.1 H NMR (nuclear magnetic resonance spectrum (200 megahertz)) CDCl.sub.3 :7.4 (d, 1H, J=5.0); 6.8 (d, 1H, J=5.0); 3.7 (br, 2H); 2.1 (s, 3H); 13C NMR CDCl.sub.3 :152.6 (d, J=229); 134.1 (d, J=8.6); 133.8 (d, J=14.5); 128.1 (d, J=27.1); 123.3, 16.4 (d, J=4.1). 3-Amino-2-fluoro-5-methylpyridine was prepared analogously from 2-fluoro-5-methyl-3-nitropyridine. This compound was obtained in 89 percent yield as white solid melting at 27.degree.-28.5.degree. C.
Elemental Analysis C.sub.6 H.sub.7 FN.sub.2 Calc.: %C, 57.1; %H, 5.59; %N, 22.2 Found: %C, 56.9, %H, 5.65; %N, 22.6
.sup.1 H NMR CDCl.sub.3 : 7.2 (d, 1H); 6.8 (d, 1H); 3.7 (br, 2H); 2.1 (s, 3H); .sup.13 C NMR CDCl.sub.3 : 151.8 (d, J=229); 134.5 (d, J=12.6); 132.2 (d, J=3.9); 129.9 (d, J=28.7); 125.8 (d, J=5.3), 17.8.
2. Preparation of 3-Amino-2-chloro-4-methoxypyridine
To a solution of 6.4 g (51 mmol) of 3-amino-4-methoxypyridine in 30 mL of 37 percent aqueous hydrochloric acid was slowly added 7.8 g of 30 percent aqueous hydrogen peroxide at room temperature with stirring. After 30 min this solution was slowly poured into 300 mL of saturated aqueous sodium bicarbonate and the resulting mixture was extracted with ether (3.times.200mL). The ethereal extracts were combined, dried over magnesium sulfate, and filtered, The fittrate was concentrated by evaporation under reduced pressure to obtain a light brown solid. This solid was purified by column chromatography (17:83 acetone:hexane) to obtain 6.54 g (81 percent of theory) of the title compound as colorless needles melting at 86.degree.-87.degree. C.
Elemental Analysis C.sub.6 H.sub.7 ClN.sub.2 O Calc.: %C, 45.4; %H, 4.45; %N, 17.7 Found: %C, 45.4; %H, 4.65; %N, 17.8
.sup.1 H NMR CDCl.sub.3 : 7.7 (d, 1H, J=5.4), 6.6 (d, 1H, J=5.4 , 4.0 (br, 2H), 3.8 (s, 3H); .sup.13 C NMR CDCl.sub.3 : 153.3, 138.5, 135.6, 129.9, 105.2, 55.9.
3-Amino-2-chloro-4-ethoxypyridine was prepared from 3-amino-4-ethoxypyridine in an analogous procedure and was obtained as a white solid melting at 72.degree.-73.degree. C.
Elemental Analysis C.sub.7 H.sub.9 ClN.sub.2 O Calc.: %C, 48.7; %H, 5.26; %N, 16.2 Found: %C, 48.9; %H, 4.98; %N, 16.5.
.sup.1 H NMR CDCl.sub.3 : 7.7 (d, 1H, J=5.4), 6.6 (d, 1H, J=5.4), 4.1 (q, 2H, J=7.0), 4.0 (br, 2H), 1.5 (t, 3H, J=7.0).
3-Amino-2-chloro-4-propoxypyridine was prepared from 3-amino-4-propoxypyridine in an analogous procedure and was obtained as a white solid melting at 46.degree.-47.degree. C.
Elemental Analysis C.sub.8 H.sub.11 ClN.sub.2 O Calc.: %C, 51.5; %H, 5.94; %N, 15.0 Found: %C, 51.8; %H, 5.97; %N, 15.2
.sup.1 H NMR CDCl.sub.3 : 7.7 (d, 1H, J=5.4), 6.6 (d, 1H, J=5.4), 4.1 (br, 2H), 4.0 (t, 2H, J=6.5), 1.84 (m, 2H), 1.0 (t, 3H, J=7.4 ).
3-Amino-2-chloro-4-(1-methylethoxy)pyridine was prepared from 3-amino-4-(1-methylethoxy)pyridine in an analogous procedure and was obtained as an amber oil.
Elemental Analysis C.sub.8 H.sub.11 ClN.sub.2 O Calc.: %C, 51.5; %H, 5.94; %N, 15.0 Found: %C, 51.1; %H, 5.87; %N, 15.4
.sup.1 H NMR CDCl.sub.3 : 7.7 (d, .sup.1 H, J=5.5), 6.6 (d, .sup.1 H, J=5.4), 4.6 (m, .sup.1 H, J=6.0), 4.0 (br, 2H), 1.34 (d, 6H, J=6.0).
3. Preparation of 3-Amino-2-ethylthio-4-methylpyridine
2-Ethylthio-4-methyl-3-nitropyridine (10.0 g, 50.4 mmol) was added slowly with stirring to a solution of 57 g (0.25 mole) of stannous chloride in 250 mL of concentrated aqueous hydrochloric acid. An exothermic reaction took place. The solution was held at 70.degree. C. for 30 min, cooled, and then poured slowly into saturated aqueous sodium bicarbonate solution. The resulting mixture was extracted with ether and the extract was dried over magnesium sulfate, filtered, and concentrated by evaporation under reduced pressure to obtain 5.8 g (68 percent of theory) of a light yellow oil that solidified upon standing. This solid was recrystallized from hexane to obtain 3.2 g of the title compound as a white solid melting at 37.degree.-38.degree. C.
Elemental Analysis C.sub.8 H.sub.12 N.sub.2 S Calc.: %C, 57.1; %H, 7.19; %N, 16.7; %S, 19.1 Found: %C, 57.3; %H, 6.88; %N, 16.8; %S, 19.0
.sup.1 H NMR CDCl.sub.3 : 7.8 (d, 1H, J=4.8), 6.7 (d, 1H, J=4.8), 3.8 (br, 2H), 3.2 (q, 2H, J=7.4), 2.1 (s, 3H), 1.3 (t, 3H, J=7.4). .sup.13 C NMR CDCl.sub.3 : 142.2, 139.5, 139.3,128.9, 122.4, 25.4, 17.0, 15.0.
4. Preparation of Methyl 3-Amino-2-chloroisonicotinate
A mixture of 18 g (118 mmol) of methyl 3-aminoisonicotinate and 12 g (60 mmol) of 1,3-dichloro-5,5-dimethylhydantoin in 1500 mL of tetrachloroethylene was warmed slowly to 80.degree. C. with stirring and held there for 3 hours. The solution was then cooled, filtered, washed with dilute aqueous sodium bicarbonate, dried over magnesium sulfate, filtered, and concentrated by evaporation under reduced pressure to obtain a dark oil. This oil was purified by careful column chromatography to give 6.7 g (30 percent of theory) of the title compound as a colorless solid melting at 91.degree.-92.degree. C.
Elemental Analysis C.sub.7 H.sub.7 ClN.sub.2 O.sub.2 Calc.: %C, 45.1; %H, 3.78; %N, 15.0 Found: %C, 45.2; %H, 3.94; %N, 15.1
.sup.1 H NMR CDCl.sub.3 : 7.7 (d, 1H, J=5.1); 7.6 (d, 1H, J=5.1; 6.2 (br, 2H); 3.9 (s, 3H); .sup.13 C NMR CDCl.sub.3 : 166.7, 141.9, 139.0, 134.7, 122.8, 116.5, 52.3.
5. Preparation of 3-Amino-4-ethyl-2-fluoropyridine
Trimethylsilyl chloride (2.2 g, (0.18 mmol) and sodium iodide (2.7 g, 0.18 mmol) were added to a solution of 3.6 g (0.15 mmol) of t-butyl N-(4-ethyl-2-fluoro-3-pyridyl)carbamate in 50 mL of dry acetonitrile with stirring at ambient temperature. After 2 hours the mixture was poured into ether and the resulting solution was washed with dilute aqueous sodium bisulfite, dried over magnesium sulfate, and filtered. The liltrate was concentrated by evaporation under reduced pressure to obtain an oil. This oil was purified by column chromatography to obtain 1.6 g (76 percent of theory) of the title compound as a gold oil.
Elemental Analysis C.sub.7 H.sub.9 FN.sub.2 Calc.: %C, 60.0; %H, 6.47; %N, 20.0 Found: %C, 59.8; %H, 6.66; %N, 20.2
.sup.1 H NMR CDCl.sub.3 : 7.4 (d, 1H, J=5.0); 6.8 (d, 1H, J=5.0); 3.7 (br, 2H); 2.45 (q, 2H, J=7.5); 1.2 (t, 3H, J=7.5).
3-Amino-4-(1-methylethyl)-2-fluoropyridine was prepared in an analogous way from t-butyl N-(4-(1-methylethyl)-2-fluoro-3-pyridyl)carbamate. This compound was obtained in 92 percent yield as a gold oil.
Elemental Analysis C.sub.8 H.sub.11 FN.sub.2 Calc.: %C, 62.3; %H, 7.19; %N, 12.3 Found: %C, 62.5; %H, 7.24; %N, 12.6.
.sup.1 H NMR CDCl.sub.3 :7.4 (d, 1H, J=5.2); 6.8 (d, 1H, J=5.1; 3.8 (br, 2H); 2.87 (m, 1H); 1.2 (d, 6H, J=6.8).
6. Preparation of t-Butyl N-(4-Ethyl-2-fluoro-3-pyridyl)carbamate
A solution of lithium diisopropylamine (LDA) was prepared from 19.3 mL (137 mmol) of diisopropylamine and 55 mL (137 mmol) of 2.5 H n-butyllithium in hexane in 250 mL of dry tetrahydrofuran at -20.degree. C. A solution of 14.4 g (62.5 mmol) of t-butyl N-(4-methyl-2-fluoro-3-pyridyl)carbamate in 80 mL of dry tetrahydrofuran was added dropwise with stirring at a rate slow enough to maintain the temperature below -60.degree. C. After a 30 min reaction period, 27 g (190 mmol) of methyl iodide was added and the solution was allowed to warm to -10.degree. C. The resulting mixture was diluted with 100 mL of aqueous ammonium chloride and 200 mL of ether and the phases were separated. The aqueous phase was washed with ether (3.times.100 mL). The organic phase and ether washes were combined, dried over magnesium sulfate, and filtered. The filtrate was concentrated by evaporation under reduced pressure to obtain a gold oil. This oil was purified by column chromatography to obtain 11.4 g (76 percent of theory) of the title compound as a white solid melting at 84.degree.-86.degree. C.
.sup.1 H NMR CDCl.sub.3 : 7.7 (d, 1H, J=5.08); 6.8 (d, 1H, J=5.08); 6.1 (br, 1H); 2.45 (q, 2H, J=7.6); 1.2 (s, 9H); 1.0 (t, 3H, J=7.6).
t-Butyl N-(4-(1-methylethyl)-2-fluoro-3-pyridyl)carbamate was prepared analogously from t-butyl N-(4-ethyl-2-fluoro-3-pyridyl)carbamate. This compound was obtained in 69 percent yield as a colorless solid melting at 60.degree.-62.degree. C.
Elemental Analysis C.sub.13 H.sub.19 FN.sub.2 O.sub.2 Calc.: %C, 61.4; %H, 7.53; %N, 11.0 Found: %C, 61.6; %H, 7.78; %N, 11.3.
.sup.1 H NMR CDCl.sub.3 : 7.9 (d, 1H, J=5.4); 7.0 (d, 1H, J=5.4); 6.0 (br, 1H); 3.2 (m, 1H); 1.4 (s, 9H); 1.2 (d, 6H, J=5.2).
7. Preparation of 3-Amino-2,4,5-trichloropyridine
Thirty percent aqueous hydrogen peroxide (3.0 g, 26 mmol) was added dropwise with stirring at 15.degree. C. to a solution of 8.0 g (49mmol) of 3-amino-4,5-dichloropyridine in 450mL of 37 percent aqueous hydrochloric acid. After 30 min another 2.6 g (23 mmol) of 30 percent aqueous hydrogen peroxide was added and the solution was allowed to slowly warm to room temperature. The resulting mixture was diluted with water, neutralized with sodium carbonate, and extracted with ether. The ethereal extract was dried over magnesium sulfate and filtered. The liltrate was concentrated by evaporation under reduced pressure to obtain a viscous oil. This oil was partially purified by column chromatography to obtain 2.5 g (26 percent of theory) of the title compound, a white solid melting at 88.degree.-90.degree. C., and 5.3 g of a mixture of the title compound and 3-amino-2,4,5,6-tetrachloropyridine.
Elemental Analysis C.sub.5 H.sub.3 Cl.sub.3 N.sub.2 Calc.: %C, 30.4; %H, 1.53; %N, 14.2 Found: %C, 30.5; %H, 1.47; %N, 14.1.
.sup.1 H NHR CDCl.sub.3 : 7.7 (s, 1H); 4.6 (br, 2H).
8. Preparation of 3-Amino-4-fluoro-2-methoxypyridine
A solution 5.0 g (26.2 mmol) of p-totuenesulfonic acid monohydrate in 150 mL of toluene was refluxed to azeotropically remove the water and was then allowed to cool. A 5.0 g (20.6 mmol) amount of t-butyl N-(4-fluoro-2-methoxy-3-pyridyl)carbamate was added and the solution was heated to reflux with stirring for 5 min. The mixture was cooled and the liquid was removed by decantation. The solid residue was partitioned between ether and saturated aqueous sodium carbonate and the organic phase was recovered, dried over magnesium sulfate, filtered, and concentrated by evaporation. The residue was purified by flash chromatography to obtain 2.7 g (91 percent of theory) of the title compound as a near-clear oil.
Elemental Analysis C.sub.6 H.sub.7 FN.sub.2 O Calc.: %C, 50.7; %H, 4.96; %N, 19.7 Found: %C, 50.9; %H, 5.26; %N, 19.1.
.sup.1 HNMR (CDCl.sub.3): 7.5 (dd, 1H, j=5.7, 7.8); 6.6 (dd, 1H, j=5.7, 9.4); 3.9 (s, 3H); 3.7 (br, 2H).
9. Preparation of t-butyl N-(4-Fluoro-2-methoxy-3-pyridinyl)carbamate
To a solution of 8 g (35.7 mmol) of t-butyl N-(2-methoxy-3-pyridyl)carbamate in 200 mL of dry tetrahydrofuran was added with stirring at -60.degree. C., 46.2 mL (78.5 mmol) of 1.7M t-butyl lithium in pentane. The resulting solution was allowed to warm slowly with stirring to -20.degree. C. over a 20 to 30 min period. It was then cooled to about -60.degree. C. and 12.2 g (38.7 mmol) of N-fluorodibenzenesulfonimide was added with stirring all at once. The mixture was allowed to warm to -20.degree. C. and was poured into 500 mL of ether. The resulting ethereal solution was washed with a mixture of 2.5 g (41.7 mmol) of acetic acid and 150 mL of water. The aqueous phase was extracted with 200 mL of ether. The ethereal extracts were combined, dried over magnesium sulfate, filtered, and concentrated by evaporation. The residue was purified by flash chromatography to obtain 6.7 g (77 percent of theory) of the title compound as a colorless solid melting at 75.degree.-77.degree. C.
Elemental Analysis C.sub.11 H.sub.15 FN.sub.2 O.sub.3 Calc.: %C, 54.5; %H, 6.24; %N, 11.6 Found: %C, 54.2; %H, 6.39; %N, 11.4.
.sup.1 H NMR (CDCl.sub.3): 7.88 (dd, 1H, j=5.8, 7.6); 6.68 (dd, 1H, j=5.8, 8.9); 5.9 (br, 1H); 3.9 (s, 3H); 1.45 (s, 9H
10. Preparation of Methyl 3-Amino-2-ethoxyisonicotinate
A solution 7.5 g (39.4 mmol) of p-toluenesulfonic acid monohydrate in 150 mL of toluene was refluxed to azeotropically remove the water. The mixture was allowed to cool and then 11.0 g (37.1 mmol) of t-butyl N-(4-carboxymethyl-2-ethoxy-3-pyridyl)carbamate was added with stirring and the solution was heated to 95.degree. C. for 15 min. The resulting mixture was cooled and the liquid was removed by decantation. The solid residue was partitioned between ether and saturated aqueous sodium carbonate. The organic phase was recovered, dried over magnesium sulfate, filtered, and concentrated by evaporation. The residue was purified by column chromatography to obtain 6.4 g (88 percent of theory) of the title compound as a light yellow solid melting at 59.degree.-60.5.degree. C.
Elemental Analysis C.sub.9 H.sub.12 N.sub.2 O.sub.3 : Calc.: %C, 55.1; %H, 6.16; %N, 14.3 Found: %C, 54.6; %H, 6.00; %N, 14.5.
.sup.1 H NMR (CDCl.sub.3): 7.3 (d, 1H, j=5.6); 7.1 (d, 1H, j=5.6); 5.9 (br, 2H); 4.3 (q, 2H, j=7.1); 3.8 (s, 3H); 1.37 (t, 3H, j=7.1).
Methyl 3-amino-2-methoxyisonicotinate, an amber oil, was prepared analogously.
Elemental Analysis C.sub.8 H.sub.10 N.sub.2 O.sub.3 Calc.: %C, 50.0; %H, 4.80; %N, 16.7 Found: %C, 50.2; %H, 5.26; %N, 16.6.
1H NMR (CDCl.sub.3): 7.3 (d, 1H, j=5.6); 7.1 (d, 1H, j=5.6); 5.9 (br, 2H); 3.96 (s, 3H); 3.8 (s, 3H).
Ethyl 3-amino-2-methoxyisonicotinate, a light yellow oil, was prepared analogously.
Elemental Analysis C.sub.9 H.sub.12 N.sub.2 O.sub.3 Calc.: %C, 55.1; %H, 6.16; %N, 14.3 Found: %C, 54.2; %H, 6,56; %N, 14.6.
.sup.1 H NMR (CDCl.sub.3): 7.3 (d, 1H, j=5.6); 7.1 (d, 1H, j=5.6); 5.9 (br, 2H); 4.28 (q, 2H, j=7.2); 3.9 (s, 3H); 1.33 (t, 3H, j=7.14).
11. Preparation of t-Butyl N-(4-Carboxymethyl-2-ethoxy -3-pyridinyl)carbamate
To a solution of 12.0 g (50.3 mmol) of t-butyl N-(2-ethoxy-3-pyridinyl)carbamate in 200 mL of dry tetrahydrofuran was added with stirring at -50.degree. C., 66 mL (111 mmol) of 1.7M t-butyl lithium in pentane. The resulting solution was allowed to warm slowly to 0.degree. C. over a 20 to 30 min period and was then cooled to -60.degree. C. and poured into 500 mL of ether saturated with crushed dry ice (carbon dioxide). The resulting mixture was acidified at room temperature with 3.0 g (50 mmol) of acetic acid and the fine white solid precipitate that formed was collected by filtration and dried under reduced pressure at 50.degree. C. to obtain 17.0 g of a lithium salt containing some tetrahydrofuran. This salt was combined with 30.0 g (211 mmol) of iodomethane in 150 mL of dry dimethyl sulfoxide and the mixture was stirred for 1 hr. It was then poured into 400 mL of water. The aqueous mixture was extracted with 500 then 200 mL of ether. The ether extracts were combined, dried over magnesium sulfate, filtered, and concentrated by evaporation. The residue was purified by column chromatography to obtain 11.5 g (77 percent of theory) of the title compound as a colorless solid melting at 94.degree.-95.5.degree. C.
Elemental Analysis C.sub.14 H.sub.20 N.sub.2 O.sub.5 Calc.: %C, 56.8; %H, 6.80; %N, 9.45 Found: %C, 56.8; %H, 7.00; %N, 9.63.
.sup.1 H NMR (CDCl.sub.3): 7.8 (d, 1H, j=5.3); 7.1 (d, 1H, j=5.3); 6.9 (br, 1H); 4.4 (q, 2H, j=7.0); 3.8 (s, 3H); 1.46 (s, 9H); 1.37 (t, 3H, j=7.0). t-Butyl N-(4-carboxyethyl-2-methoxy-3-pyridinyl)carbamate, a colorless solid melting at 40.degree.-41.degree. C., was prepared analogously.
Elemental Analysis C.sub.14 H.sub.20 N.sub.2 O.sub.5 Calc.: %C, 56.8; %H, 6.80; %N, 9.45 Found: %C, 56.6; %H, 6.76;% N, 9.26.
.sup.1 H NMR (CDCl.sub.3): 7.9 (d, 1H, j=5.3); 7.1 (d, 1H, j=5.25); 6.9 (br, 1H); 4.27 (q, 2H, j=7.15); 3.96 (s, 3H); 1.45 (s, 9H); 1.33 (t, 3H, j=7.14).
t-Butyl N-(4-Carboxymethyl-2-methoxy-3-pyridinyl)carbamate, a colorless solid melting at 107.degree.-108.degree. C., was obtained analogously.
Elemental Analysis C.sub.13 H.sub.18 N.sub.2 O.sub.5 Calc.: %C, 55.3; %H, 6.43; %N, 9.92 Found: %C, 55.5; %H, 6.22; %N, 10.1.
1H NMR (CDCl.sub.3): 7.9 (d, 1H, j=5.3); 7.1 (d, 1H, j=5.4); 6.9 (br, 1H); 3.97 (s, 3H); 1.46 (s, 9H).
12. Preparation of t-Butyl N-(4-Chloro-2-ethoxy-3-pyridinyl)carbamate
To a solution of 15 g (63 mmol) of t-butyl N-(2-ethoxy-3-pyridinyl)carbamate in 175 mL of dry tetrahydrofuran was added with stirring at -60.degree. C., 78 mL (132 mmol) of 1.7M t-butyl lithium in pentane. The resulting solution was allowed to warm to -10.degree. C. over a 30 min. period and was then cooled to -60.degree. C. A 22.3 g (94 mmol) amount of hexachloroethane was added all at once with stirring and the mixture are allowed to warm to ambient temperature. It was then diluted with 600 mL of ether and the resulting solution was washed with 150 mL of water, dried over magnesium sulfate, filtered, and concentrated by evaporation. The residue was purified by column chromatography to obtain 11.1 g (65 percent of theory) of the title compound as a colorless solid melting at 73.degree.-74.degree. C.
Elemental Analysis C.sub.12 H.sub.17 ClN.sub.2 O.sub.3 : Calc.: %C, 52.9; %H, 6.28; %N, 10.3 Found: %C, 53.0; %H, 6.30; %N, 10.3.
.sup.1 H NMR (CDCl.sub.3): 7.88 (d, 1H, j=5.5); 6.93 (d, 1H, j=5.5); 6.0 (br, 1H); 4.4 (q, 2H, j=7.0); 1.5 (s, 9H); 1.39 (t, 3H, j=7.0.).
13. Preparation of t-Butyl N-(2-Ethoxy-3-pyridinyl)carbamate
To a solution of 38.1 g (0.28 mol) of 3-amino-2-ethoxypyridine in 400 mL of dry dioxane was added with stirring 60 g (0.28 mol) of di-t-butyl dicarbonate and the solution was slowly heated to reflux over a 4 hr period. The resulting solution was cooled below reflux and another 5.0 g (23 mmol) of di-t-butyl dicarbonate was added with stirring and the mixture was reheated at reflux for 1 hr. The volatiles were removed by evaporation under reduced pressure and the residue obtained was purified by column chromatography to obtain 58.3 g (89 percent of theory) of the title compound as a colorless oil.
Elemental Analysis C.sub.12 H.sub.18 N.sub.2 O.sub.3 Calc.: %C, 60.5; %H, 7.61; %N, 11.8 Found: %C, 59.7; %H, 9.03; %N, 11.9.
.sup.1 H NMR (CDCl.sub.3 ): 8.2 (broad d, 1H, j=7.0 ); 7.7 (d, 1H, j=5.0); 6.9 (br, 1H); 6.8 (dd, 1H, j=5.0, 5.0), 4.4 (q, 2H, j=7.1); 1.47 (s, 9H); 1.36 (t, 3H, j=7.1).
14. Preparation of 3-Amino-4-ethoxy-2-fluoropyridine
To a solution of 19 g (74 mmol) of t-butyl N-(4-ethoxy-2-fluoro-3-pyridinyl)carbamate and 12.2 g (81.5 mmol) of sodium iodide in 400 mL of dry acetonitrile was added with stirring 8.9 g (81.5 mmol) of trimethylsilyl chloride. The mixture was allowed to react for 4 hr and then a 100 mL solution of aqueous sodium bicarbonate was added with stirring. The resulting mixture was extracted with 1 L of ether and the ether extract was dried over magnesium sulfate, filtered, and concentrated by evaporation. The residue was purified by column chromatography to obtain 6.3 g (55 percent of theory) of the title compound as a colorless solid melting at 76.degree.-77.degree. C.
Elemental Analysis C.sub.7 H.sub.9 FN.sub.2 O Calc.: %C, 53.5; %H, 5.81; %N, 17.9 Found: %C, 54.3; %H, 6.44; %N, 17.7.
.sup.1 H NMR (CDCl.sub.3): 7.5 (d, 1H, j=5.74); 6.5 (d, 1H, j=5.64); 4.1 (q, 2H, j=7.0); 3.6 (br, 2H); 1.4 (t, 3H, j=6.9).
3-Amino-2-fluoro-4-methoxypyridine, a colorless solid melting at 48.degree.-50.degree. C., was prepared analogously.
Elemental Analysis C.sub.6 H.sub.7 FN.sub.2 O Calc.: %C, 50.7; %H, 4.96; %N, 19.7 Found: %C, 50.9; %H, 5.13; %N, 19.9.
.sup.1 H NMR (CDCl.sub.3): 7.5 (d, 1H, j=5.57 ); 6.63 (d, 1H, j=5.47); 3.8 (s, 3H); 3.7 (br, 2H).
3-Amino-2-fluoro-4-propoxypyridine, a colorless oil, was prepared analogously.
Elemental Analysis C.sub.8 H.sub.11 FN.sub.2 O Calc.: %C, 55.5; %H, 6.51; %N, 16.5 Found: %C, 56.7; %H, 6.66; %N, 16.2.
.sup.1 H NMR (CDCl.sub.3): 7.4 (d, 1H, j=5.61; 6.5 (d, 1H, j=5.71); 4.5 (t, 2H, j=6.5); 3.7 br, 2H); 1.8 (m, 2H, j=7.3); 1.0 (t, 3H, j=7.4).
3-Amino-2-fluoro-4-(1-methylethoxy)pyridine, a gold oil, was prepared analogously.
Elemental Analysis C.sub.8 H.sub.11 FN.sub.2 O Calc.: %C, 55.5; %H, 6.51; %N, 16.5 Found: %C, 56.9; %H, 6.69; %N, 16.4.
.sup.1 H NMR (CDCl.sub.3): 7.5 (d, 1H, j=5.57); 6.6 (d, 1H, j=5.71); 4.5 (m, 1H, j=6.0); 3.6 (br, 2H); 1.3 (d, 6H, j=6.1).
15. Preparation of t-Butyl N-(4-ethoxy-2-fluoro-3-pyridinyl)carbamate
To a solution of 18.5 g (131 mmol) of 4-ethoxy-2-fluoropyridine in 300 mL of dry tetrahydrofuran at -78.degree. C. was added slowly, with stirring and cooling to maintain the temperature below -65.degree. C., 58 mL of 2.5M butyl lithium in hexane. The mixture was allowed to react for 1 hr and then the resulting slurry was poured into 1300 mL of ether containing excess powdered dry ice (carbon dioxide). The fine white precipitate that formed was collected by filtration and dried under reduced pressure for 90 min. The hygroscopic solid obtained was taken into 700 mL of t-butanol and 68 g (0.24 mol) of diphenyl phosphoryl azide was added with stirring. This mixture was slowly warmed to reflux for 2 hr during which time there was a vigorous evolution of nitrogen. The resulting slurry was filtered and the filtrate was diluted with 800 mL of dichloromethane. The organic phase was separated, washed with water (2.times.100 mL), and concentrated by evaporation to obtain a semi-solid residue. This was dissolved in fresh dichloromethane and the solution was dried over magnesium sulfate, filtered, and concentrated by evaporation. The residue was purified by column chromatography to obtain 19.5 g (63 percent of theory) of the title compound as a colorless solid melting at 130.degree.-131.degree. C.
Elemental Analysis C.sub.12 H.sub.17 FN.sub.2 O.sub.3 Calc.: %C, 56.2; %H, 6.69; %N, 10.9 Found: %C, 56.1; %H, 6.99; %N, 11.3.
.sup.1 H NMR (CDCl.sub.3): 7.85 (d, 1H, j=5.7); 6.6 (d, 1H, j=5.7); 6.0 (br, 1H); 4.1 (q, 2H, j=7.0); 1.4 (t, 3H, j=6.9); 1.35 (t, 3H, j=7.0).
t-Butyl N-(2-fluoro-4-(1-methylethoxy)-3-pyridinyl)carbamate, a colorless solid melting at 80.degree.-81.5.degree. C., was obtained analogously.
Elemental Analysis C.sub.13 H.sub.19 FN.sub.2 O.sub.3 Calc.: %C, 57.8; %H, 7.09; %N, 10.4 Found: %C, 57.9; %H, 6.94; %N, 10.7.
.sup.1 H NMR (CDCl.sub.3): 7.9 (d, 1H, j=5.9); 6.7 (d, 1H, j=5.96); 6.0 (br, 1H); 4.6 (m, 1H, j=6.1); 1.45 (s, H); 1.35 (d, 6H, j=6.1).
t-Butyl N-(2-fluoro-4-propoxy-3-pyridinyl) carbamate, a colorless solid melting at 84.degree.-86.degree. C., was obtained analogously.
Elemental Analysis C.sub.13 H.sub.19 FN.sub.2 O.sub.3 Calc.: %C, 57.8; %H, 7.09; %N, 10.4 Found: %C, 57.8; %H, 7.37; %N, 10.5.
.sup.1 H NMR (CDCl.sub.3): 7.9 (d, 1H, j=5.8); 6.7 (d, 1H, j=5.8); 5.8 (br, 1H); 4.0 (t, 2H, j=6.5); 1.83 (m, 2H, j=7.36); 1.46 (s, 9H); 1.0 (t, 3H, j=7.5).
16. Preparation of 4-Ethoxy-2-fluoropyridine
To a solution of 60.5 g (0.31 mol) of 3,5-dichloro-4-ethoxy-2-fluoropyridine and 32.2 g (0.32 mol) of sodium acetate in 400 mL of ethanol in a 1 L stirred steel Parr bomb was added 3 g of 5 percent palladium on carbon catalyst. The reactor was charged with 500 pounds per square inch gauge (3550 kiloPascals) of hydrogen and heated with stirring to 100.degree. C. for 4 hr. The mixture was cooled, filtered, and concentrated by evaporation. The residue was dissolved in ether and the resulting solution was dried over magnesium sulfate, filtered, and concentrated by evaporation. The residue was purified by bulb to bulb distillation (60.degree.-80.degree. C. at 0.5 mm Hg (67 Pascals) to obtain 18.5 g (42 percent of theory) of the title compound as a colorless oil which solidified upon standing and melted at 35.degree.-36.degree. C.
Elemental Analysis C.sub.7 H.sub.8 NO Calc.: %C, 59.6; %H, 5.71; %N, 9.92 Found: %C, 59.2; %H, 5.97; %N, 9.95.
.sup.1 H NMR (CDCl.sub.3): 7.9 (d, 1H, j=5.8); 6.6 (m, 1H); 6.3 (d, 1H, j=2.2); 4.0 (q, 2H, j=7.0); 1.4 (t, 3H, j=7.0).
2-Fluoro-4-methoxypyridine, a colorless oil boiling at 119.degree.-122.degree. C. at 30 mm Hg (4.0 kiloPascals), was prepared analogously.
Elemental Analysis C.sub.6 H.sub.6 FNO: Calc.: %C, 59.6; %H, 5.71; %N, 9.92 Found: %C, 59.2; %H, 5.97; %N, 9.95.
.sup.1 H NMR (CDCl.sub.3): 8.0 (d, 1H, j=5.9); 6.7 (m, 1H); 6.4 (d, 1H, j=2.1); 3.9 (s, 3H).
2-Fluoro-4-(1-methylethoxy)pyridine, a colorless oil, was obtained analogously.
Elemental Analysis C.sub.8 H.sub.10 FNO Calc.: %C, 61.9; %H, 6.50; %N, 9.03 Found: %C, 61.5; %H, 6.59; %N, 9.32.
.sup.1 H NMR (CDCl.sub.3): 8.0 (d, 1H, j=5.9); 6.6 (dd, 1H, j=4.5, 1.4); 6.33 (d, 1H, j=2.0); 4.0 (t, 2H, j=6.6); 1.8 (m, 2H, j=7.3); 1.0 (t, 3H, j=7.3).
2-Fluoro-4-propoxypyridine, a colorless oil, was obtained analogously.
Elemental Analysis C.sub.8 H.sub.10 FNO Calc.: %C, 61.9; %H, 6.50; %N, 9.03 Found: %C, 61.0; %H, 7.50; %N, 9.09.
.sup.1 H NMR (CDCl.sub.3): 8.0 (d, 1H, j=5.9); 6.6 (m, 1H); 6.3 (d, 1H, j=2.2); 4.57 (m, 1H, j=6.1); 1.3 (d, 6H, j=6.1).
17. Preparation of 3,5-Dichloro-4-ethoxy-2-fluoropyridine
To a solution of 70.2 g (0.38 mol) of 3,5-dichloro-2,4-difluoropyridine in 600 mL of ethanol was slowly added with stirring a solution of sodium ethoxide in ethanol prepared from 16 g (0.40 mol) of sodium hydride (60 percent in mineral oil, hexane washed) in 200 mL of ethanol. The mixture was allowed to stir overnight and the brown solution obtained was filtered through powdered cellulose and concentrated by evaporation under reduced pressure. The residue was partitioned between 500 mL of ether and 400 mL of water. The organic phase was recovered, dried over magnesium sulfate, filtered, and concentrated by evaporation. The residue was distilled to obtain 62 g (84 percent of theory) of the title compound as a colorless oil having a boiling point of 175.degree.-180.degree. C. at 0.4 mm Hg (53 Pascals).
Elemental Analysis C.sub.7 H.sub.6 Cl.sub.2 FN Calc.: %C, 43.3; %H, 3.12; %N, 7.22 Found: %C, 40.0; %H, 2.92; %N, 6.66.
.sup.1 H NMR (CDCl.sub.3): 8.04 (s, 1H); 4.3 (q, 2H, j=7.0); 1.48 (t, 3H, j=7.1).
3,5-Dichloro-2-fluoro-4-methoxypyridine, a colorless oil, was obtained analogously.
.sup.1 H NMR (CDCl.sub.3): 8.1 (S, 1H); 4.88 (m, 1H, j=6.1); 1.4 (d, 6H, j=6.1).
3,5-Dichloro-2-fluoro-4-(1-methylethoxy)pyridine, a colorless oil, was obtained analogously. .sup.1 H NMR (CDCl.sub.3): 8.0 (s, 1H); 4.88 (m, 1H, j=6.1); 1.4 (d, 6H, j=6.1).
3,5-Dichloro-2-fluoro-4-propoxypyridine, a colorless oil, was obtained analogously. .sup.1 H NMR (CDCl.sub.3): 8.1 (s, 1H); 4.2 (t, 2H, j=6.7); 1.86 (m, 2H, j=7.1); 1.1 (t, 3H, j=7.3).
18. Preparation of N-(2-Chloro-4-methoxy-3-pyridinyl)-7-fluoro-5-methoxy[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide
To a solution of 5.4 g (33.8 mmol) of 3-amino-2-chloro-4-methoxypyridine and 3.0 g (11.3 mmol) of 2-chlorosulfonyl-7-fluoro-5-methoxy[1,2,4]triazolot1,5-c]pyrimidine in 20 mL of dry acetonitrile was added with stirring 0.91 mL (11.3 mmol) of dry pyridine and 0.16 mL (2.3 mmol) of dry dimethyl sulfoxide (DMSO). After 2 hours the resulting slurry was poured into a mixture of 200 mL of water and 800 mL of dichloromethane and the resulting mixture was stirred for 1 hour. The organic phase was recovered, dried over magnesium sulfate, filtered, and concentrated by evaporation under reduced pressure. The residue remaining was purified by flash column chromatography to obtain 1.6 g (38 percent of theory) of the title compound as a white solid melting at 187.degree.-188.degree. C.
Elemental Analysis C.sub.12 H.sub.10 ClFN.sub.6 O.sub.4 S Calc.: %C, 37.1; %H, 2.59; %N, 21.2; %S, 8.25 Found: %C, 37.3; %H, 2.46; %N, 21.5; %S, 8.22
.sup.1 H NMR DMSO-d.sub.6 : 10.7 (br, 1H), 8.2 (d, 1H, J=5.7), 7.4 (s, H), 7.1 (d, 1H, J=5.7), 4.2 (s, 3H), 3.4 (s, 3H).
19. Preparation of N-(2-chloro-4-methoxy-3-pyridyl)-5,7-dimethoxy[1,2,4]triazplo[1,5-c]pyrimidine-2-sulfonamide
To a solution of 0.60 g (1.5 mmol) of N-(2-chloro-4-methoxy-3-pyridinyl)-7-fluoro-5-methoxy[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide in 20 mL of dimethyl sulfoxide was added with stirring 0.24 g (3.4 mmol) of potassium methoxide in 2.4 mL of dry methanol. After 1 hour 5 mL of acetic acid was added and the solution taken up in 400 mL of dichloromethane. The resulting solution was washed with water (6.times.150 mL), dried over magnesium sulfate, filtered, and concentrated by evaporation under reduced pressure to obtain 270 mg (20 percent of theory) of the title compound as a white solid melting at 197.degree.-199.degree. C. with decomposition.
Elemental Analysis C.sub.13 H.sub.13 ClN.sub.6 O.sub.4 S Calc.: %C, 39.0; %H, 3.27; %N, 21.0 Found: %C, 39.0; %H, 3.40; %N, 20.9
.sup.1 H NMR DMSO-d.sub.6 : 10.6 (br, 1H); 8.2 (d, 1H, J=5.7 ); 7.1 (d, 1H, J=5.7); 6.7 (s, 1H); 4.2 (s, 3H); 3.9 (s, 3H); 3.4 (s, 3H).
20. Preparation of N-(4-Ethoxy-3-pyridinyl)-5-methoxy-7-methyl[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide
2-Chlorosulfonyl-5-methoxy-7-methyl[1,2,4]triazolo[1,5-c]pyrimidine (1.5 g, 5.7 mmol) was added to a solution of 0.8 g (5.7 mmol) of 3-amino-4-ethoxypyridine in 30 mL of dry pyridine in portions over 10 minutes with stirring. After 16 hours the reaction mixture was poured into 400 mL of dichloromethane. The resulting mixture was washed with 150 mL of water, dried over magnesium smlfate, and filtered. The liltrate was combined with 5 g of silica gel and the mixture was concentrated by evaporation under reduced pressure. The resulting silica plug was placed onto a 200 g silica gel column and eluted with dichloromethane containing increasing amount of ethanol. The product fractions were combined and concentrated by evaporation under reduced pressure and the solid obtained was dried to obtain 0.75 g (36 percent of theory) of the title compound as a white solid melting at 184.degree.-186.degree. C.
Elemental Analysis C.sub.14 H.sub.16 N.sub.6 O.sub.4 S Calc.: %C, 46.2; %H, 4.43; %N, 23.1; %S, 8.08 Found: %C, 46.5; %H, 4.37; %N, 22.8; %S, 7.98
.sup.1 H NMR (DMSO-d6): 10.5 (br, 1H); 8.3 (s, 1H); 8.26 (d, 1H, J=5.6); 7.4 (s, 1H); 7.0 (d, 1H, J=5.6); 4.2 (s, 3H); 3.9 (q, 2H, J=7.0); 2.5 (s, 1H); 1.0 (t, 3H, J=7.0).
21. Evaluation of Postemergence Herbicidal Activity
Seeds of the desired test plant species were planted in Grace-Sierra MetroMix.RTM. 306 planting mixture, which typically has a pH of 6.0 to 6.8 and an organic matter content of about 30 percent, in plastic pots with a surface area of 64 square centimeters. When required to ensure good germination and healthy plants, a fungicide treatment and/or other chemical or physical treatment was applied. The plants were grown for 7-21 days in a greenhouse with an approximately 15 hr photoperiod which was maintained at about 23.degree.-29.degree. C. during the day and 22.degree.-28.degree. C. during the night. Nutrients and water were added on a regular basis and supplemental lighting was provided with overhead metal halide 1000 Watt lamps as necessary. The plants were employed for testing when they reached the first or second true leaf stage.
A weighed amount, determined by the highest rate to be tested, of each test compound was placed in a 20 mL glass vial and was dissolved in 4 mL of a 97:3 v/v (volume/volume) mixture of acetone and dimethyl sulfoxide to obtain concentrated stock solutions. If the test compound did not dissolve readily, the mixture was warmed and/or sonicated. The concentrated stock solutions obtained were diluted with an aqueous mixture containing acetone, water, isopropyl alcohol, dimethyl sulfoxide, Atplus 411F crop oil concentrate, and Triton X-155 surfactant in a 48.5:39:10:1.5:1.0:0.02 v/v ratio to obtain spray solutions of known concentration. The solutions containing the highest concentration to be tested were prepared by diluting 2 mL aliquots of the stock solution with 13 mL of the mixture and lower concentrations were prepared by dilution of appropriate smaller portions of the stock solution. Approximately 1.5 mL aliquots of each solution of known concentration were sprayed evenly onto each of the test plant pots using a DeVilbiss atomizer driven by compressed air pressure of 2 to 4 psi (140 to 280 kiloPascals) to obtain thorough coverage of each plant. Control plants were sprayed in the same manner with the aqueous mixture. In this test an application rate of 1 ppm results in the application of approximately 1 g/Ha.
The treated plants and control plants were placed in a greenhouse as described above and watered by sub-irrigation to prevent wash-off of the test compounds. After 2 weeks the condition of the test plants as compared with that of the untreated plants was determined visually and scored on a scale of 0 to 100 percent where 0 corresponds to no injury and 100 corresponds to complete kill. Some of the compounds tested, application rates employed, plant species tested, and results are given in Tables 2 and 2A.
TABLE 2__________________________________________________________________________POSTEMERGENCE HERBICIDAL ACTIVITY WildCpd. Rate, Cockle- Jimson- Morning- Velvet- Field Buck- Black- Giant Johnson-No. ppm bur weed glory leaf Pansy wheat grass foxtail grass__________________________________________________________________________ 1 1000 15 85 15 65 -- 30 55 0 15 2 250 55 40 70 40 50 70 35 0 0 3 125 90 85 90 100 89 85 85 90 70 4 250 100 100 85 88 80 88 75 30 60 5 250 90 80 85 95 90 85 80 85 75 6 2000 80 85 0 85 30 80 50 60 15 7 1000 80 50 85 85 80 88 50 80 20 8 31.3 90 -- 95 98 100 85 80 78 70 9 250 90 -- 75 85 100 90 80 80 7810 125 90 80 70 85 70 75 80 40 9011 2000 75 80 75 70 98 70 80 78 7512 1000 80 90 90 75 90 80 98 75 9013 7.81 100 90 50 80 98 90 70 70 8014 15.6 99 83 100 100 0 85 75 20 9515 7.81 90 88 85 75 70 75 60 60 8516 15.6 100 -- 90 90 70 85 70 80 9017 62.5 85 90 85 95 70 90 70 30 6018 15.6 80 -- 80 80 60 80 75 50 7519 7.81 85 -- 100 80 40 80 60 50 7820 7.81 98 -- 95 80 0 80 40 0 7521 7.81 90 70 70 98 70 70 60 20 8522 15.6 85 85 75 75 45 80 40 40 6023 15.6 98 80 80 90 80 90 80 35 --24 15.6 100 80 100 50 70 90 70 80 9025 31.3 100 95 85 100 70 100 78 60 9026 15.6 98 100 85 90 20 100 70 40 027 31.3 80 80 80 80 0 80 0 0 4528 500 15 80 70 80 70 70 85 80 9029 15.6 100 93 75 65 80 95 45 40 8330 31.3 75 80 70 98 70 75 95 10 10031 500 80 80 70 80 90 75 85 75 8532 125 90 80 70 85 40 80 8 o 45 7533 125 70 80 80 80 85 85 75 30 4034 15.6 99 80 80 80 100 98 20 45 8035 31.3 90 85 88 85 88 85 90 85 8836 125 70 88 90 85 100 86 90 85 8437 62.5 85 90 90 89 100 80 89 85 8538 15.6 88 80 85 88 75 88 75 80 8039 250 75 70 85 95 95 95 90 90 9040 81 83 95 70 83 100 75 60 40 7541 31.3 70 80 85 93 70 93 80 20 8342 31.3 100 70 75 80 100 100 70 70 8543 125 85 80 88 100 75 85 50 50 8544 500 50 75 85 85 50 85 70 20 7545 31.3 -- -- 90 88 70 80 50 85 9046 31.3 -- -- 88 88 88 88 75 70 9547 62.5 75 80 85 80 80 78 80 65 8048 7.81 90 0 85 80 80 80 70 70 9049 15.6 100 88 88 80 80 80 40 40 8550 15.6 100 88 90 85 70 84 35 30 8551 31.3 90 90 88 88 90 80 88 90 8052 15.6 90 -- 85 70 75 85 55 70 8553 15.6 90 -- 88 85 88 88 55 70 10054 500 90 -- 90 85 85 90 70 70 8555 250 95 98 90 80 80 90 0 40 6056 62.5 90 80 80 75 80 75 65 20 7057 31.3 20 80 40 85 70 75 90 70 8558 500 60 80 60 80 95 80 80 80 8059 62.5 40 80 60 80 90 80 75 70 9060 500 85 75 80 88 90 70 80 90 7561 62.5 60 85 80 85 95 90 90 90 9063 15.6 70 70 80 90 85 85 90 40 8864 500 100 95 75 85 85 85 65 50 8565 250 100 95 90 80 80 75 60 60 6066 250 100 90 85 75 98 85 60 60 3067 1000 99 70 45 40 85 75 45 10 6068 1000 100 80 90 75 83 93 70 45 8069 62.5 97 55 70 95 99 90 45 70 770 1000 77 83 95 75 70 70 80 65 2071 500 100 90 95 85 83 50 50 65 072 62.5 100 80 100 90 90 85 0 70 10073 31.3 98 75 80 75 90 80 75 60 9074 1000 85 75 80 80 85 83 75 70 9975 250 100 75 75 90 90 80 85 100 7576 1000 80 75 85 50 40 70 70 75 60__________________________________________________________________________
TABLE 2A__________________________________________________________________________POSTEMERGENCE HERBICIDAL ACTIVITY Wild ROXCpd. Rate, Cockle- Lambs- Morning- Velvet- Field Buck- Black- Giant OrangeNo. ppm bur quarter glory leaf Pansy wheat grass foxtail Sorghum__________________________________________________________________________ 77 500 98 60 75 75 90 65 70 75 78 78 62.5 100 60 100 100 75 80 90 80 90 79 31.3 100 55 88 85 55 87 70 75 75 80 15.6 100 90 85 85 87 88 90 85 8 81 1.95 88 80 85 85 90 80 85 70 70 82 15.6 90 60 90 85 88 80 85 30 75 83 62.5 90 90 80 -- 70 -- 75 85 70 84 500 78 65 75 60 80 50 75 85 70 85 2 50 90 90 80 70 60 78 80 80 85 86 500 88 60 90 70 80 70 70 75 90 87 62.5 100 80 85 80 80 80 60 70 85 88 62.5 90 60 100 75 80 85 35 40 85 89 15.6 100 75 90 90 80 75 40 40 78 90 250 100 85 90 90 75 88 90 80 100 91 125 100 85 85 80 80 80 85 75 88 92 125 100 85 78 90 75 85 85 50 78 93 31.3 95 60 85 85 75 80 80 45 80 95 125 100 65 80 75 60 70 70 70 65 96 7.8 100 50 98 70 60 70 40 20 70 97 500 100 80 85 85 40 85 70 60 40 98 250 100 60 80 80 70 80 50 20 80 99 250 90 50 85 85 85 85 80 85 90100 62.5 90 90 85 90 90 95 90 95 95101 15.6 100 70 80 80 60 70 90 70 80102 125 100 50 80 70 50 80 30 80 70103 500 100 65 80 70 70 80 85 80 85104 62.5 100 60 90 90 75 70 90 30 85105 62.5 80 20 90 60 70 70 65 60 98107 31.3 70 70 80 75 70 70 95 95 98108 1.3 100 70 98 98 70 80 65 30 80110 250 90 70 90 65 80 90 80 75 80112 125 98 -- 85 85 90 80 90 50 95113 500 85 -- 80 70 70 50 75 30 80114 250 100 -- 80 80 70 85 75 20 75115 62.5 85 100 80 90 90 90 98 50 90116 62.5 100 -- 90 75 80 80 80 60 80117 31.2 90 100 90 80 90 80 90 35 90118 15.6 100 -- 80 75 85 80 80 30 90119 15.6 90 -- 80 85 90 85 90 30 90120 15.6 95 -- 80 90 95 85 85 90 90121 31.2 85 -- 75 80 95 70 75 0 8122 62.5 90 -- 80 75 85 75 80 50 90123 7.8 100 -- 75 90 90 80 80 70 85124 15.6 85 -- 85 85 90 90 88 90 95125 500 100 70 90 75 78 80 80 50 90126 125 100 90 75 80 80 70 75 55 85127 3.9 98 90 95 85 80 60 80 65 75128 3.9 100 78 90 78 83 70 85 0 75129 7.8 99 80 90 78 75 95 98 0 75130 15.6 100 78 100 83 75 95 85 5 65131 15.6 100 85 90 98 75 80 95 70 90132 62.5 100 78 100 93 80 80 85 65 88133 15.6 98 90 95 98 83 83 83 65 78134 15.6 95 78 88 98 75 93 95 55 78135 62.5 100 88 75 93 65 95 98 65 78136 15.6 100 88 100 78 75 95 98 20 75137 15.6 100 -- 80 99 65 83 90 65 95138 31.2 100 -- 98 75 88 98 95 40 95139 31.2 100 -- 98 80 75 95 98 50 70140 125 100 -- 99 80 80 98 98 70 78141 15.6 100 -- 80 95 75 98 99 20 93142 15.6 98 80 80 78 70 83 99 70 85143 15.6 98 -- 100 85 78 88 98 75 95144 31.2 100 -- 85 85 78 75 98 65 75145 62.5 100 -- 90 0 95 80 60 70 90146 62.5 100 -- 90 70 80 80 50 50 90147 3.9 99 80 75 95 75 90 70 78 88148 1.95 95 98 95 98 60 83 78 65 93149 15.6 100 99 78 78 178 78 90 55 80150 15.6 100 100 100 98 80 78 98 60 78151 7.8 100 98 100 78 75 80 95 50 78152 31.2 98 85 98 85 78 70 98 5 83153 15.6 100 95 90 80 78 -- 70 50 78154 15.6 100 95 95 80 78 90 70 75 78155 62.5 100 -- 98 98 85 98 93 70 85156 15.6 100 -- 95 98 75 95 90 10 65157 31.2 100 -- 78 90 70 70 98 70 70158 31.2 90 -- 70 70 78 80 98 75 85159 15.6 98 -- 98 75 60 75 95 50 83160 15.6 100 -- 98 75 50 75 93 0 90161 31.2 100 -- 98 85 70 80 95 65 80162 15.6 100 -- 100 78 80 78 98 60 80163 31.2 90 -- 90 70 75 78 80 25 70164 31.2 99 -- 70 70 78 70 95 25 65165 15.6 95 90 85 70 85 85 80 20 80166 15.6 100 88 90 90 85 90 80 90 90167 15.6 100 100 100 90 85 90 88 80 88168 9.8 98 78 100 95 90 80 78 70 78169 15.6 100 75 90 90 85 90 90 70 78170 31.2 100 95 75 80 88 80 80 80 90__________________________________________________________________________
22. Evaluation of Preemergence Herbicidal Activity
Seeds of the desired test plant species were planted in a soil matrix prepared by mixing a loam soil which was composed of about 43 percent silt, 19 percent clay, and 38 percent sand and had a pH of about 8.1 and an organic matter content of about 1.5 percent and sand in a 70 to 30 ratio. The soil matrix was contained in plastic pots with a surface area of 161 square centimeters. When required to ensure good germination and healthy plants, a fungicide treatment and/or other chemical or physical treatment was applied.
A weighed amount, determined by the highest rate to be tested, of each test compound was placed in a 20 mL glass vial and was dissolved in 8 mL of a 97:3 v/v (volume/volume) mixture of acetone and dimethyl sulfoxide to obtain concentrated stock solutions. If the test compound did not dissolve readily, the mixture was warmed and/or sonicated. The stock solutions obtained were diluted with a 99.9:0.1 mixture of water and Tween.RTM. 155 surfactant to obtain application solutions of known concentration. The solutions containing the highest concentration to be tested were prepared by diluting 4 mL aliquots of the stock solution with 8.5 mL of the mixture and lower concentrations were prepared by dilution of appropriate smaller portions of the stock solution. A 2.5 mL aliquot of each solution of known concentration was sprayed evenly onto the soil of each seeded pot using a Cornwall 5.0 mL glass syringe fitted with a TeeJet TN-3 hollow cone nozzle to obtain thorough coverage of the soil in each pot. Control pots were sprayed in the same manner with the aqueous mixture. A highest application rate of 4.48 Kg/Ha is achieved when 50 mg of test compound is employed.
The treated pots and control pots were placed in a greenhouse with an approximately 15 hr photoperiod which was maintained at about 23.degree.-29.degree. C. during the day and 22.degree.-28.degree. C. during the night. Nutrients and water were added on a regular basis and supplemental lighting was provided with overhead metal halide 1000 Watt lamps as necessary. The water was added by top-irrigation. After 3 weeks the condition of the test plants that germinated and grew as compared with that of the untreated plants that germinated and grew was determined visually and scored on a scale of 0 to 100 percent where 0 corresponds to no injury and 100 corresponds to complete kill or no germination. Some of the compounds tested, application rates employed, plant species tested, and results are given in Table 3.
TABLE 3__________________________________________________________________________PREEMERGENCE HERBICIDAL ACTIVITY Wild Barn-Cpd. Rate, Morning- Velvet- Buck- Black yard Giant Johnson-No. Kg/Ha glory Pigweed leaf wheat grass Grass foxtail grass__________________________________________________________________________2 1.12 40 50 75 60 70 603 0.56 85 80 80 80 70 90 95 204 1.12 90 100 85 98 10 95 75 755 2.24 60 75 85 85 25 98 98 208 0.56 50 90 80 90 90 90 98 509 1.12 8 95 85 90 8 98 98 9010 1.12 85 90 95 90 98 5 75 --11 4.48 50 100 98 30 100 100 60 10013 0.035 90 100 95 -- 90 65 90 9014 0.14 80 98 95 90 85 95 80 --15 0.14 90 85 90 90 5 90 90 9016 0.018 40 100 90 100 80 90 80 --17 0.035 80 98 95 50 70 90 20 --18 0.035 80 95 80 50 90 95 30 --19 0.018 80 90 90 0 50 80 60 --20 0.035 90 90 80 80 80 95 50 --21 0.018 80 98 80 70 60 95 60 --22 0.035 90 85 95 80 70 85 20 --23 0.14 80 90 95 90 30 0 60 6024 0.070 90 100 70 90 90 98 100 9025 0.070 60 100 80 75 60 98 20 8526 0.035 90 100 85 5 90 90 60 8027 0.035 60 100 95 90 95 98 80 8028 0.056 50 98 98 80 98 98 98 7529 0.070 80 90 80 85 75 100 75 9030 0.14 95 90 95 85 98 98 50 9831 1.12 50 75 50 30 75 75 50 7532 0.56 98 98 85 90 98 98 50 9833 0.28 90 95 10 95 75 60 40 8034 0.070 75 100 90 90 50 50 70 8035 0.070 80 95 85 80 100 70 90 9036 0.28 5 60 85 90 100 98 90 9037 0.018 80 80 75 90 90 98 80 8538 0.035 90 98 95 98 90 85 95 9839 0.035 40 90 85 98 80 90 85 9040 0.018 90 100 90 -- 40 60 75 9041 0.28 90 100 98 -- 95 90 95 9042 0.035 90 100 95 -- 50 40 60 9043 0.56 90 30 75 90 95 98 60 9045 0.035 70 98 80 88 40 70 85 8546 0.28 40 90 60 70 o 60 65 8547 0.14 40 90 80 87 95 75 Po 8048 0.009 60 95 70 75 80 90 70 9049 0.070 90 98 85 95 75 90 78 9050 0.14 90 98 5 95 65 98 65 9051 0.070 88 90 90 80 95 80 85 8852 0.035 90 97 75 90 65 80 70 9053 0.009 90 85 85 88 85 90 75 8854 0.14 90 85 85 90 60 70 45 8055 0.56 90 90 65 90 70 65 30 8056 0.28 5 80 75 80 40 40 30 6557 0.56 75 80 85 50 80 55 80 9058 1.12 65 95 80 55 95 70 75 9059 0.14 75 90 90 90 75 70 0 9060 1.12 100 90 65 70 98 80 65 8061 0.14 90 98 88 90 10 70 90 8063 0.14 70 90 85 90 95 95 80 9564 1.12 80 80 70 80 98 60 75 9565 0.56 80 60 70 50 99 80 80 9066 0.56 90 70 60 70 90 90 90 7067 0.28 20 70 30 65 90 70 30 8068 0.28 65 80 50 85 100 90 80 9069 0.070 85 90 75 90 60 70 70 7570 1.12 30 50 40 20 30 85 95 5071 2.24 75 90 50 40 50 90 70 6072 0.070 50 90 50 60 50 50 60 9073 0.035 70 70 70 80 85 95 90 9074 1.12 60 90 50 50 50 70 50 9075 0.56 80 95 80 90 80 85 95 5077 0.28 40 50 50 -- 70 70 90 --78 0.070 85 95 95 -- 95 98 90 --79 0.28 85 75 90 -- 85 85 95 --80 0.070 80 85 98 -- 98 20 95 --81 0.070 90 90 90 -- 95 80 85 --82 0.28 95 50 80 -- 100 95 60 --83 0.28 90 80 70 -- 85 95 60 --84 2.24 85 90 65 -- 90 65 70 --85 1.12 75 50 75 -- 80 75 60 --87 0.070 80 60 85 -- 80 95 85 --88 0.14 80 80 90 -- 80 95 80 --89 0.14 85 75 85 -- 85 90 80 --90 0.070 90 90 95 -- 95 85 70 --91 0.070 85 85 90 -- 95 90 95 --92 0.56 75 80 90 -- 95 95 75 --93 0.14 85 75 90 -- 98 95 25 --94 0.28 60 40 25 -- 70 75 70 --97 1.12 90 85 70 -- 60 70 50 --98 1.12 78 90 85 -- 65 80 75 --101 0.035 85 80 85 -- 85 85 75 --102 0.28 35 70 80 -- 90 95 80 --103 0.28 35 65 80 -- 85 85 60 --104 0.070 85 80 95 -- 95 75 50 --105 0.14 90 90 85 -- 90 70 75 --108 0.14 90 74 95 -- 85 90 75 --110 0.56 60 70 78 -- 90 100 95 --112 0.14 80 95 85 -- -- 100 78 --113 1.12 20 95 90 -- -- 60 50 --114 1.12 90 95 80 -- -- 78 55 --115 0.28 90 85 85 -- -- 98 90 --116 0.28 90 70 90 -- -- 80 60 --117 0.28 85 95 90 -- -- 95 90 --118 0.14 90 70 80 -- -- 60 70 --119 0.070 90 95 95 -- -- 70 85 --120 0.070 90 98 95 -- -- 80 90 --121 1.12 90 100 80 -- -- 98 78 --122 0.56 90 55 85 -- 95 80 75 --123 0.14 90 80 90 -- -- 95 95 --124 0.14 90 95 95 -- -- 90 80 --125 0.56 85 90 80 -- -- 85 70 --126 0.28 85 95 90 -- -- 78 78 --127 0.14 85 95 90 -- 80 95 90 --128 0.007 85 70 80 -- 100 95 90 --129 0.14 85 98 90 -- 90 95 95 --130 0.14 85 95 90 -- 98 80 80 --131 0.14 85 98 85 -- 100 95 95 --132 0.14 95 80 85 -- 90 90 78 --133 0.14 95 80 85 -- 90 90 78 --134 0.070 90 70 85 -- 90 95 70 --135 0.14 90 75 90 -- 90 70 50 --136 0.070 90 70 85 -- 95 70 50 --137 0.035 80 100 80 -- 80 95 78 --138 0.14 80 100 85 -- 90 78 70 --139 0.14 90 70 90 -- 90 90 90 --140 0.28 90 70 90 -- 95 85 75 --141 0.035 90 80 80 -- 78 90 65 --142 0.14 90 90 90 -- 90 90 90 --143 0.14 90 78 80 -- 95 90 90 --144 0.14 90 78 80 -- 99 85 75 --145 0.14 60 100 78 -- 60 90 85 --146 0.28 80 90 80 -- 70 95 80 --147 0.035 90 85 90 -- 80 95 85 --148 0.035 90 90 90 -- 80 100 95 --149 0.070 90 85 80 -- 90 85 80 --150 0.14 90 80 90 -- 90 100 90 --151 0.070 90 90 90 -- 90 85 80 --152 0.14 90 78 90 -- 98 90 78 --153 0.070 80 95 80 -- 78 95 90 --154 0.14 90 90 80 -- 85 100 95 --155 0.070 85 100 85 -- 90 98 75 --156 0.070 85 95 90 -- 75 90 70 --157 0.14 90 90 90 -- 95 50 75 --158 0.28 85 95 90 -- 90 70 90 --159 0.14 90 100 90 -- 90 80 70 --160 0.14 90 95 85 -- 85 90 60 --161 0.14 90 90 85 -- 90 80 70 --162 0.070 80 90 90 -- 90 60 40 --163 0.56 90 80 90 -- 95 80 80 --164 0.28 90 50 85 -- 95 80 60 --165 0.070 90 95 95 -- 90 80 90 --166 0.070 90 80 95 -- 85 85 80 --167 0.035 90 80 90 -- 80 95 95 --168 0.035 90 85 98 -- 90 99 90 --169 0.018 90 75 90 -- 85 100 75 --170 0.14 80 98 75 -- 85 98 90 --__________________________________________________________________________
Claims
  • 1. An N-pyridinyl[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide compound of the formula: ##STR6## wherein R represents (C.sub.1 -C.sub.3)alkyl optionally monosubstituted with F, Cl, or OCH.sub.3 or represents CH.sub.2 CF.sub.3 ;
  • Y and Z, each independently represents H, F, Cl, Br, I, OCH.sub.3, OC.sub.2 H.sub.5, C.sub.2 H.sub.5, or CH.sub.3, said CH.sub.3 being optionally mono to completely substituted with F;
  • V represents H, COR', CO.sub.2 R", or CONR"'.sub.2 ;
  • A and B each independently represents H, R', OR', OCH.sub.2 CH.sub.2 Cl, OCH.sub.2 CH.sub.2 OCH.sub.3, S(O).sub.n R', F, Cl, Br, I, CN, NO.sub.2, C.sub.6 H.sub.5, CO.sub.2 R", or CONR'".sub.2 with the proviso that not more than one of A and B represents H;
  • D represents H, F, Cl, Br, I, CF.sub.3, or CH.sub.3 ;
  • n represents 0, 1, or 2;
  • R' represents (C.sub.1 -C.sub.4)alkyl optionally singly to completely substituted with fluorine;
  • R" represents (C.sub.1 -C.sub.4) alkyl, (C.sub.3 -C.sub.4) alkenyl, or (C.sub.3 -C.sub.4 ) alkynyl,
  • R"' represents H or (C.sub.1 -C.sub.4)alkyl; and when V represents H, the agriculturally acceptable salts thereof.
  • 2. A compound according to claim 1 wherein V represents H.
  • 3. A compound according to claim 1 wherein R represents methyl or ethyl.
  • 4. A compound according to claim 1 wherein one of Y and Z represents CH.sub.3, F, Cl, Br, I, or OCH.sub.3, and the other represents H.
  • 5. A compound according to claim 4 wherein R represents methyl or ethyl, Y represents methyl, and Z represents hydrogen or wherein R represents methyl or ethyl, Y represents hydrogen, and Z represents a halogen or methoxy.
  • 6. A compound according to claim 1 wherein A represents CH.sub.3, O(C.sub.1 -C.sub.3)alkyl, F, Cl, Br, or I; B represents F, Cl, Br, I, CH.sub.3, C.sub.2 H.sub.5, CF.sub.3, O(C.sub.1 -C.sub.3)alkyl, OCH(CH.sub.3)CF.sub.3, OCH.sub.2 CH.sub.2 F, OCH.sub.2 CHF.sub.2, or CO.sub.2 (C.sub.1 -C.sub.3)alkyl; and D represents H.
  • 7. A compound according to claim 6 wherein A represents Br, Cl, F, or OCH.sub.3, B represents CH.sub.3, OCH.sub.3, OC.sub.2 H.sub.5, OC.sub.3 H.sub.7 (n), OC.sub.3 H.sub.7 (i), OCH(CH.sub.3)CF.sub.3, or OCH.sub.2 CH.sub.2 F, and D represents H; or wherein A represents OCH.sub.3 or OC.sub.2 H.sub.5, B represents CO.sub.2 (C.sub.1 -C.sub.2)alkyl, Br, Cl, or F, and D represents H.
  • 8. The compound according to claim 1: N-(2-fluoro-4-methyl-3-pyridinyl)-5,8-dimethoxy[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide.
  • 9. The compound according to claim 1: N-(2-chloro-4-methyl-3-pyridinyl)-5-methoxy-8-chloro[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide.
  • 10. The compound according to claim 1: N-(2-chloro-4-methoxy-3-pyridinyl)-5-ethoxy-7-methyl[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide.
  • 11. The compound according to claim 1: N-(2-chloro-4-(1-methylethoxy)-3-pyridinyl)-5-ethoxy-7-methyl[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide.
  • 12. An herbicidal composition comprising an herbicidally effective amount of an N-pyridinyl[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide compound of the formula: ##STR7## wherein R represents (C.sub.1 -C.sub.3)alkyl optionally monosubstituted with F, Cl, or OCH.sub.3 or represents CH.sub.2 CF.sub.3 ;
  • Y and Z, each independently represents H, F, Cl, Br, I, OCH.sub.3, OC.sub.2 H.sub.5, C.sub.2 H.sub.5, or CH.sub.3, said CH.sub.3 being optionally mono to completely substituted with F;
  • V represents H, COR', CO.sub.2 R", or CONR"'.sub.2 ;
  • A and B each independently represents H, R', OR', OCH.sub.2 CH.sub.2 Cl, OCH.sub.2 CH.sub.2 OCH.sub.3, S(O)nR', F, Cl, Br, I, CN, NO.sub.2, C.sub.6 H.sub.5, CO.sub.2 R", or CONR"'.sub.2 with the proviso that not more than one of A and B represents H;
  • D represents H, F, Cl, Br, I, CF.sub.3, or CH.sub.3 ;
  • n represents 0, 1, or 2;
  • R' represents (C.sub.1 -C.sub.4)alkyl optionally singly to completely substituted with fluorine;
  • R" represents (C.sub.1 -C.sub.4)alkyl, (C.sub.3 -C.sub.4)alkenyl, or (C.sub.3 -C.sub.4) alkynyl,
  • R"' represents H or (C.sub.1 -C.sub.4)alkyl; and
  • when V represents H, the agriculturally acceptable salts thereof in admixture with an agriculturally acceptable adjuvant or carrier.
  • 13. A composition according to claim 12 wherein V represents H.
  • 14. A composition according to claim 12 wherein R represents methyl or ethyl.
  • 15. A composition according to claim 12 wherein one of Y and Z represents CH.sub.3, F, Cl, Br, I, or OCH.sub.3, and the other represents H.
  • 16. A composition according to claim 15 wherein R represents methyl or ethyl, Y represents methyl, and z represents hydrogen or wherein R represents methyl or ethyl, Y represents hydrogen, and Z represents a halogen or methoxy.
  • 17. A composition according to claim 12 wherein A represents CH.sub.3, O(C.sub.1 -C.sub.3)alkyl, F, Cl, Br, or I; B represents F, Cl, Br, I, CH.sub.3, C.sub.2 H.sub.5, CF.sub.3, O(C.sub.1 -C.sub.3)alkyl, OCH (CH.sub.3)CF.sub.3, OCH.sub.2 CH.sub.2 F, OCH.sub.2 CHF.sub.2, or CO.sub.2 (C.sub.1 -C.sub.3) alkyl; and D represents H.
  • 18. A composition according to claim 17 wherein A represents Br, Cl, F, or OCH.sub.3, B represents CH.sub.3, OCH.sub.3, OC.sub.2 H.sub.5, OC.sub.3 H.sub.7 (n), OC.sub.3 H.sub.7 (i), OCH(CH.sub.3)CF.sub.3, or OCH.sub.2 CH.sub.2 F, and D represents H; or wherein A represents OCH.sub.3 or OC.sub.2 H.sub.5, B represents CO.sub.3 (C.sub.1 -C.sub.2)alkyl, Br, Cl, or F, and D represents H.
  • 19. The composition according to claim 12 wherein the compound is N-(2-fluoro-4-methyl-3-pyridinyl)-5,8-dimethoxy[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide.
  • 20. The composition according to claim 12 wherein the compound is N-(2-chloro-4-methyl-3-pyridinyl)-5-methoxy-8-chloro[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide.
  • 21. The composition according to claim 12 wherein the compound is N-(2-chloro-4-methoxy-3-pyridinyl)-5-ethoxy-7-methyl[1,2,4]triazolo[1,5-c]-pyrimidine-2-sulfonamide.
  • 22. The composition according to claim 12 wherein the compound is N-(2-chloro-4-(1-methylethoxy)-3-pyridinyl)-5-ethoxy-7-methyl[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide.
  • 23. A method of controlling undesirable vegetation which comprises applying to said vegetation or to the locus thereof an herbicidally effective amount of an N-pyridinyl[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide compound of the formula: ##STR8## wherein R represents (C.sub.1 -C.sub.3)alkyl optionally monosubstituted with F, Cl, or OCH.sub.3 or represents CH.sub.2 CF.sub.2 ;
  • Y and Z, each independently represents H, F, Cl, Br, I, OCH.sub.3, OC.sub.2 H.sub.5, C.sub.2 H.sub.5, or CH.sub.3, said CH.sub.3 being optionally mono to completely substituted with F;
  • V represents H, COR', CO.sub.2 R", or CONR"'.sub.2 ;
  • A and B each independently represents H, R', OR', OCH.sub.2 CH.sub.2 Cl, OCH.sub.2 CH.sub.2 OCH.sub.3, S(O).sub.n R', F, Cl, Br, I, CN, NO.sub.2, C.sub.6 H.sub.5, CO.sub.2 R", or CONR'".sub.2 with the proviso that not more than one of A and B represents H;
  • D represents H, F, Cl, Br, I, CF.sub.3, or CH.sub.3 ;
  • n represents 0, 1, or 2;
  • R' represents (C.sub.1 -C.sub.4)alkyl optionally singly to completely substituted with fluorine;
  • R"represents (C.sub.1 -C.sub.4 alkyl, (C.sub.3 -C.sub.4)alkenyl, or (C.sub.3 -C.sub.4)alkynyl,
  • R"' represents H or C.sub.1 -C.sub.4)alkyl; and when V represents H, the agriculturally acceptable salts thereof.
  • 24. A method according to claim 23 wherein V represents H.
  • 25. A method according to claim 23 wherein R represents methyl or ethyl.
  • 26. A method according to claim 23 wherein one of Y and z represents CH.sub.3, F, Cl, Br, I, or OCH.sub.3, and the other represents H.
  • 27. A method according to claim 26 wherein R represents methyl or ethyl, Y represents methyl, and Z represents hydrogen or wherein R represents methyl or ethyl, Y represents hydrogen, and Z represents a halogen or methoxy.
  • 28. A method according to claim 23 wherein A represents CH.sub.3, O(C.sub.1 -C.sub.3)alkyl, F, Cl, Br, or I; B yrepresents F, Cl, Br, I, CH.sub.3, C.sub.2 H.sub.5, CF.sub.3, O(C.sub.1 -C.sub.3)alkyl, OCH(CH.sub.3)CF.sub.3, OCH.sub.2 CH.sub.2 F, OCH.sub.2 CHF.sub.2, or CO.sub.2 (C.sub.1 -C.sub.3)alkyl; and D represents H.
  • 29. A method according to claim 28 wherein A represents Br, Cl, F, or OCH.sub.3, B represents CH.sub.3, OCH.sub.3, OC.sub.2 H.sub.5, OC.sub.3 H.sub.7 (n), OC.sub.3 H.sub.7 (i), OCH(CH.sub.3)CF.sub.3, or OCH.sub.2 CH.sub.2 F, and D represents H; or wherein A represents OCH.sub.3 or OC.sub.2 H.sub.5, B represents CO.sub.2 (C.sub.1 -C.sub.2)alkyl, Br, Cl, or F, and D represents H.
  • 30. The method according to claim 23 wherein the compound is N-(2-fluoro-4-methyl-3-pyridinyl)-5,8-dimethoxy[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide.
  • 31. The method according to claim 23 wherein the compound is N-(2-chloro-4-methyl-3-pyridinyl)-5-methoxy-8-chloro[1,2,4]triazolo[1,5-c]Pyrimidine-2-sulfonamide.
  • 32. The method according to claim 23 wherein the compound is N-(2-chloro-4-methoxy-3-pyridinyl)-5-ethoxy-7-methyl[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide.
  • 33. The method according to claim 23 wherein the compound is N-(2-chloro-4-(1-methylethoxy)-3-pyridinyl)-5-ethoxy-7-methyl[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide.
  • 34. The method according to claim 23 wherein the compound is applied postemergently.
  • 35. The method according to claim 23 wherein a selectively effective N-pyridinyl[1,2,4]triazolo[1,5-c]-pyrimidine-2-sulfonamide compound is applied in a selectively effective amounm in the presence of a desirable crop.
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Continuation in Parts (1)
Number Date Country
Parent 273514 Jul 1994