United States Patent (19) 11 Patent Number: 4,992,091 Vinogradoff Et Al
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United States Patent (19) 11 Patent Number: 4,992,091 Vinogradoff et al. (45) Date of Patent: Feb. 12, 1991 54 SUBSTITUTED 4,650,892 3/1987 Kleschick et al. .................. 544/25 PYRAZOLO(1,5-APYRIMIDINE-2-SUL 4,740,233. 4/1988 Kleschick et al. ...................... 71/92 FONAMIDES AND COMPOSITIONS AND FOREIGN PATENT DOCUMENTS METHODS OF CONTROLLING UNDESRED VEGETATION 244097A 11/1987 European Pat. Off. 0.009943 4/1970 Japan ................................... 544/28 75) Inventors: Anna P. Vinogradoff, Concord; 951652 3/1964 United Kingdom . William A. Kleschick, Martinez, both of Calif. OTHER PUBLICATIONS Kirkpatricket al., J. Med. Chem., vol. 20, p. 386 (1977). 73) Assignee: The Dow Chemical Company, Chemical Abstracts, vol. 86 (1977): AN 83509x. Midland, Mich. Broadbent et al., J. Chem. Soc., 1965, pp. 3369-3372. 21 Appl. No.: 884,696 Primary Examiner-Donald G. Daus (22 Filed: Jul. 11, 1986 Assistant Examiner-E. Bernhardt Attorney, Agent, or Firm-D. Wendell Osborne; Merlin 51) Int. Cl..................... C07D 487/04; A01N 43/54 B. Davey 52 U.S. Cl. ........................................ 71/92; 544/250; 544/281; 548/375; 548/376; 558/396 57 ABSTRACT 58 Field of Search ....................... 544/281, 250, 251; Novel compounds, e.g. 3-cyano-5,7-dimethyl-N-(2,6- 71/92 dichlorophenyl)pyrazolo 1,5-alpyrimidine-2-sulfona mide and their use as herbicides and/or for the suppres 56 References Cited sion of nitrification of ammonium nitrogen in soil. U.S. PATENT DOCUMENTS 4,349,378 9/1982 Cliff et al. ............................. 71/103 12 Claims, No Drawings 4,992,091 1. 2 -continued SUBSTITUTED A (III) B PYRAZOLO(1,5-APYRIMIDINE-2-SULFONA N N MDES AND COMPOSITIONS AND METHODS OF 5 CONTROLLING UNDESRED VEGETATION C N N SO2NHAr BACKGROUND OF THE INVENTION H D In recent years there has been a great deal of effort 10 wherein Ar represents an aromatic (substituted or un directed to the development of sulfonamides having substituted) or heteroaromatic (substituted or unsubsti herbicidal activity and several of these compounds have tuted) ring system. reached the stage of commercialization, i.e., chlorosul DETALEED DESCRIPTION OF THE furon and sulfometuron methyl. These compounds ex INVENTION hibit both preemergence and postemergence activity 15 The aromatic or heteroaromatic ring systems include, against undesirable vegetation and, in addition, have a for example, phenyl; 1- or 2-napthyl; 2-, 3- or 4-pyridyl; low toxicity to animals. The compounds of the prior art 2- or 3-thienyl; 2- or 3-furyl; 2-, 4- or 5-thiazolyl; 2-, 4 may be depicted as follows: or 5-imidazolyl; 2-, 4- or 5-oxazolyl; 3-, 4- or 5-isothiazo 20 lyl; 3-, 4- or 5-isoxazolyl; 3-, 4- or 5-pyrazolyl: 2-benz thiazolyl; 2-benzoxazolyl; 2-benzimidiazolyl and 1 benztriazolyl. Typical examples of substituents found Ar-SO2NHCNH-Ar' on the aromatic or heteroaromatic ring systems may be one, more than one or a combination of the following: wherein Ar is usually a benzene derivative and Ar' is 25 halo (F, Cl, Br, I), C1-C4 alkyl, C1-C2 mono-, di-, tri-, usually a pyrimidine or symmetrical triazine derivative. tetra- or perhaloalkyl, phenyl, hydroxy, alkoxy, ha loalkoxy, phenoxy, substituted phenoxy, heteroaryloxy, SUMMARY OF THE INVENTION substituted heteroaryloxy, amino, alkylamino, dialkyl We have now found that compounds having the for amino, nitro, alkylthio, haloalkylthio, alkylsulfinyl, ha 30 loalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, substi mula: tuted or unsubstituted phenylthio, substituted or unsub stituted phenylsulfinyl, substituted or unsubstituted A. (1) phenylsulfonyl, cyano, carboxylic acids (and deriva tives of carboxylic acids such as esters derived from N N 35 readily available alcohols and amides derived from ammonia or readily available primary and secondary S. SO2NHAr amines), sulfonic acids (and derivatives of sulfonic acids C n N -N-- such as sulfonates derived from readily available alco D hols and sulfonamides derived from ammonia or readily available primary or secondary amines), formyl, alkyl Wherein Ar represents an aromatic (substituted or un carbonyl, haloalkylcarbonyl, phenylcarbonyl, substi substituted) or heteroaromatic (substituted or unsubsti tuted phenylcarbonyl, oximino, oxime ethers, carbinols tuted) ring system wherein the substituents are electron (and carbinol derivatives such as ethers and esters de withdrawing functional groups in combination with rived from readily available alkylating agents and car other organic functional groups are exceptionally active 45 boxylic acids respectively) and mercaptoalkyl (and de rivatives of mercaptoalkyl groups such as thioethers herbicides and are readily produced. The aromatic ring and thioesters derived from readily available alkylating may be monocyclic containing six carbon atoms or agents and carboxylic acids respectively). bicyclic containing ten carbon atoms. The heteroaro The substituents on the pyrazolopyrimidine fragment matic ring may be monocyclic containing five or six 50 of structure I are represented by A, B, C and D. Substit atoms or bicyclic containing nine or ten atoms. The uents A, B, C and D may be H, alkyl, haloalkyl, hy heteroatoms present in the heteroaromatic ring may be droxy, alkoxy, haloalkoxy, phenyl, substituted phenyl, a combination of one or more atoms such as nitrogen, halo (F, Cl, Br, I), alkylthio, phenyhthio, amino (includ oxygen or sulfur. ing alkyl or aryl substituted amino), carboxylic acids 55 and esters. In addition, two adjacent substituents (i.e., A In addition certain derivatives of compounds of gen and B or B and C) may be bonded together in a satu eral formula (I) also exhibit herbicidal activity and are rated five, six or seven-membered cyclic structure. Ex effective in beneficially regulating the growth of crops amples of such cyclic structures could be represented and have the general formulas: by A and B or B and C equal to -(CH2)- where n=3, 4 or 5. These cyclic structures may also contain heteroatoms (e.g., N, O or S) as in the case where A and A (IE) B or B and C is equal to -(CH2).O- where n=2 or 3. In the above substituents alkyl, alkenyl, alkynyl and BS4N N alkoxy in each instance have from 1 to 10 carbon atoms. Sa 65 Substituent D may be H, CO2Et, CN and halo (F, Cl, Br, I). C N - N-so Preferred compounds of the invention have the gen eral formula: 4,992,091 4. A. R2 A (II) R1 R3 Saf N N N 5 c1s 11-son R4 C N 1's--so D R5 D R 10 wherein Ar and A, B, C and D are as described above wherein R represents halo (F, Cl, Br, I), -NO2, for compound I and R represents alkyl, alkenyl, alky phenyl, --OAr, -CF3, -OCF3, -OCF2CC12H, nyl, phenylalkyl, substituted phenylalkyl, acyl, alkoxy --OCH2CF3, -SCF3, -SCF2CF2H, -SCF2CC2H, carbonyl, phenoxycarbonyl, dialkylaminocarbonyl, al -SOCF3, - SOCF2CF2H, -SOCF2CC12H, kylsulfonyl, phenylsulfonyl, alkylthiocarbonyl, or phe --SO2CF2H, -SO2CF2CCl2H, -SR6, -SOR6, 5 nylthiocarbonyl wherein alkyl, alkenyl and alkynyl are --SO2R6, CN, -COOR7, -CONH2, -CONHR8, as above defined. -CONHR8(R9), -SO3R8 and -SO3CH2CF3; R2 and Preferred derivatives of the invention have the gen R represent H, halo (F, Cl, Br, I), C1-C4 alkyl, COOR7 eral formula: and -OR8; R3 is H; and R5 represents H, C1-C4 alkyl, 20 A. R2 N N R1 R3 N 25 C Sa N 1-1-0. R R4 D RS R6OR6 and -CR6R6SR6 and wherein Ar represents wherein A, B, C, D, R, R2, R3, R and R5 are as de substituted or unsubstituted aryl or substituted or un scribed above for I and R represents C1-C4 alkyl, allyl, substituted heteroaryl, R6 represents H, aryl or C1-C4 30 benzyl, -COR10, -CO2R10, -CONR210, -COSR10, alkyl, R7 represents C1-C6 alkyl, alkenyl, alkynyl, aryl, and -SO2R10 wherein R10 is C1-C6 alkyl, phenyl, sub stituted phenyl or C1-C2 haloalkyl. substituted alkyl or substituted aryl and R8 and R9 indi Most preferred derivatives of the invention have the vidually represent C1-C4 alkyl; and A, B and C repre general formula: sent H, C1-C4 alkyl, C1-C4 alkoxy, halo (F, Cl, Br, I), or 35 A and B or B and C can be joined to form a cycloalkyl ring (i.e., -(CH2)- wherein n is 3 or 4) or A and B or A. R2 B R1 B and C can be joined to form a ring containing a het a N eroatom (i.e., -O(CH2)- wherein n is 2 or 3); and D represents H, CO2Et, CN and halo (F, Cl, Br, I). S. SON Most preferred compounds of the invention have the C N -N-- general formula: D R5 wherein A, B, C, D, R, R2 and R5 are as described A. R2 45 above for I and R is COR10 wherein R10 is C1-C4 alkyi. B R1 Specifically preferred derivatives of this embodiment N N of the invention include all of the specifically preferred compounds listed previously in other embodiments of Sa SO2NH the invention wherein the hydrogen of the sulfonamide C N -N-- 50 portion of their structures (SO2NH) has been replaced D Rs with any of the following groups: 1. COCH3. wherein R represents C1-C4 alkyl, halo (F, Cl, Br, I), COCH2CH3. -NO2, -SR6, -SOR6, -SO2R6, -COOR7 or CF3; COCH2CH2CH3. R2 represents H, halo (F, Cl, Br, I), C1-C4 alkyl, and 55 COCH(CH3)2. COOR7; and R5 represents H, C1-C4 alkyl, C1-C4 alk COCH2CH2CH2CH3. oxy, halo (F, Cl, Br, I), CH2OR6, phenyl, NO2 and COCH2CH(CH3)2. COOR7 wherein R6 represents C1-C4 alkyl, and R7 COCH2C(CH3)3. represents C1-C4 alkyl, C1-C4 alkenyl, C1-C4 alkynyl, COCH2C6H5. 2-ethoxyethyl and 2-pyridylmethyl and A, B and C COcyclo-C6H11. independently represent H, halo (F, Cl, Br, I), C1-C4 10. COCH-CHC6H5. ... COC6H5. alkyl or C1-C4 alkoxy, and D independently represents 12.