PROCESS FOR THE PREPARATION OF HERBICIDAL SULFONAMIDES DERIVED FROM SUBSTITUTED 2-AMINO-1,2,4 TRIAZOLO (1,5-A) PYRIMIDINES AND NOVEL INTERMEDIATES PROVIDED THEREIN

Abstract: Sulfonamides derived from substituted 2-amino-1,2,4-­ triazolo[1,5-a]pyrimidines are prepared by reacting a desired sulfonamide with dimethyl N-cyanodithioiminocarbonate in the presence of a base followed by reaction with an excess of hydrazine and then a 1,3-dicarbonyl compound. The resulting products have a plurality of herbicidal uses.

Description: PROCESS FOR THE PREPARATION OF HERBICIDAL SULFONAMIDES DERIVED FROM SUBSTITUTED 2-AMINO-1,2,4-TRIAZOLO[1,5-a] PYRIMIDINES AND NOVEL INTERMEDIATES PROVIDED THEREIN Compounds of general structure I EMI1.1 wherein Ar represents an aromatic (substituted or unsubstituted) or heteroaromatic (substituted or unsubstituted) ring system exhibit herbicidal activity against a variety of weed species. While some of the compounds in this family may be prepared by a conventional, convergent approach via the requisite substituted 2-amino-l, 2,4-triazolo [1,5-a] pyrimidine, many analogs cannot be made following this approach. The highly insoluble nature of many of the appropriate substituted 2-amino-1,2,4-triazolo[1,5-a] pyrimidines prohibit their reaction with the less reactive and less stable aromatic sulfonyl chlorides. We have found a new method for the preparation of compounds of type I which eliminate most of the limitations of methodology which had been previously described. The method of this invention also provides novel intermediates as described more fully hereinafter. The novel procedure for the preparation of compounds of formula I is illustrated in Scheme I. The starting aromatic sulfonyl chlorides II and sulfonamide III are commercially available or may be prepared from appropriate starting materials as known in the art. In accordance with this invention the sulfonamides III are reacted with dimethyl N-cyanodithioiminocarbonate in the presence of a base in a solvent. Bases which are effective in this transformation include tertiary amine (i,e. triethylamine) or alkali metal hydroxides, alkoxides or carbonates (i.e. NaOH, NaOCH3 or K2CO3). Appropriate solvents include acetone, methyl ethyl ketone acetonitrile or tetrahydrofuran (THF). The reaction may be run at temperatures ranging from ambient temperature to reflux. The products of this transformation (IV) may be isolated directly as their salts and converted to their neutral species by acidification. In some instances the salt may be used directly in subsequent transformations without purification or conversion to the corresponding neutral species. Compound IV may be reacted with an excess of hydrazine to form the intermediate 1,2,4-triazoles V. This reaction is generally carried out in solvents such as acetonitrile, ThF, DMF, or DMSO at ambient temperature although higher temperatures may be employed to increase the rate of reaction. The amount of excess bydrazine utilized in this transformation range from 5 to 400 mole percent. The final step in this sequence for the conversion of compound V to I may be carried out as generally outlined in "Heterocyclic Systems with Bridgehead Nitrogen Atoms", Part Two, W. L. Mosby, Interscience Publishers, 1961, p. 878. A wide variety of 1,3-dicarbonyl compounds may be used in this reaction which may be run under acidic (i.e. acetic acid as a solvent), neutral (i.e. DMF as a solvent) or basic conditions (i.e. using alkali metal alkoxides or carbonates in polar aprotic solvents such as DMF or DMSO). Scheme I EMI3.1 EMI4.1 In examples where unsymmetrical 1,3-dicarbonyl compounds are employed in the process outlined in Scheme I, the possibility of obtaining two different isomeric condensation products exists. Often the appropriate choice of reaction conditions (i.e. acidic or basic) allows for control of the regiochemistry of the annulation process. In cases where ss-ketoesters or malonic esters are used in the last step of the process described above, the products contain hydroxy groups (i.e. I where X and/or Z is OH). These products may be subjected to further transformations involving conversion of the hydroxy groups to chlorine with phosphorous oxychloride. The resulting halo substituted compounds are capable of undergoing reaction with nucleophiles to affect nucleophilic substitution of the halogen. This procedure is highly useful in the preparation of alkoxy, alkylthio and amino substituted heterocyclic ring systems An alternative procedure for the synthesis of intermediates of general structure IV is illustrated in equation 1. The starting materials (VI) may be prepared from aromatic sulfonamides by known art (i.e. F. L. Merchan, Synthesis, 984 (1982); R. Gompper, et al., Chem. Ber., 99, 2885, 2990 (1966)). These intermediates may be reacted with cyanamide in the presence of base. Bases include tertiary amines and alkali metal alkoxides, hydroxides and carbonates. This reaction is most frequently carried out in acetonitrile or THF at temperatures ranging from ambient temperature to reflux. EMI5.1 In certain instances intermediates VI may convert to their corresponding mono or dichloro derivatives (i.e. VII and VIII respectively). This may be accomplished by known art (i.e. E. Kuhle, et al., Angew, Chem Int. Ed. Engl., 6, 649 (1967)). These intermediates may then be advantageously used in a manner analogous to VI in the synthesis of compounds of general structure I. EMI5.2 Compounds advantageously prepared by the process of this invention have the general formula: EMI6.1 wherein R1 represents halo (F, C1, Br, I), -NO2, phenyl, OAr, -CF3, -OCF3, -OCF2CF2H, -OCF2CCl2H, -OCH2CF3, -SCF3, -SCF2CF2H, -SCF2CCl2H, -SOCF3, -SOCF2CF2H, -SOCF2CCl2H, -SO2CF3, -SO2CF2CF2H, -SO2CF2CClH, -SR6, -SOR6, -SO2R6 -CN, -COOR7, -CONH2, -CONHR8, BCONR8(R9), -SO3R8 and -SO3CH2CF3; R2 and R4 represent H, halo (F, Cl, Br, I), C1-C4 alkyl, COOR7 and -OR8; R3 is H; and R5 represents H, C1 to C4 alkyl, halo (F, Cl, Br, I), NO2, CF3, -OCF3, -OCF2CF2H, -OCF2CC12H, -OCH2CF3, -SCF3, -SCF2CF2H, -SCF2CCl2H, SOCF3, -SOCF2CF2H, SOCF2CCl2H, -SO2CF3, -SO2CF2CF2H, SO2CF2CCl2H, -SR6, -SOR6, SO2R6, -CN, -COOR7, -COHR8, -CONR8(R9), -SO3R8, -SO3CH2CF3, -CR6R6OR6 and -CR6R6SR6 wherein Ar represents substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl, R6 represents H, aryl or C1-C4 alkyl, R7 represents C1-C6 alkyl, alkenyl,alkynyl, aryl, substituted alkyl or substituted aryl and R8 and R9 individually represent C1-C4 alkyl; and X, Y and Z represent H, C1-C4 alkyl, C1-C4 alkoxy halo (F, C1, Br, I), or X and Y or Y and Z can be joined to form a cycloalkyl ring (i.e., -(CH2)n- wherein n is 3 or 4) or X and Y or Y and Z can be joined to form a ring containing a heteroatom (i.e., -O(CH2)n- wherein n is 2 or 3). In this specification aryl and heteroaryl refer to 5- or 6-membered aromatic or heteraromatic ring systems wherein the substituents are, individually and preferably, hydrogen, halogen, nitro, C1-C4 alkyl, C1-C4 mono- or polyhaloalkyl, C1-C4 alkoxy, C1-C4 mono- or polyhaloalkoxy or amino. The following examples illustrate the invention. Example 1 N'-Cyano-N-(2-nitrophenylsulfonyl)-S -methylisothiourea. A mixture of 2.02 g (10.0 mmol) of 2-nitrobenzene-sulfonamide, 1.46 g (10.0 mmol) of dimethyl N-cyanodithioiminocarbonate and 1.38 g (10.0 mmol) of powdered, anhydrous K2CO3 in 16 ml of acetone was heated at reflux for 20 hours. The reaction mixture was filtered and the solid collected was washed several times with acetone. The filtrate was evaporated and the orange oily residue was triturated with ether to afford a solid. The solid was collected by filtration, washed with ether and suspended in 10 ml of 1N HC1. After stirring for 1 hour the solid was collected by filtration, washed with water and dried to yield 1.65 g (55 percent) of the desired product as a cream colored solid, mp 122"C (decomposition). IR and 1H NMR spectra were consistent with the assigned structure. Analysis: Calculated for C H N 0 S : C, 36.00; H, 2.69; N, 18.66; S, 21.35. Found: C, 36.10; H, 2.74; N, 18.72; S, 21.22. Example 2 N-(5-Amino-I,24-triazol-3-yl )-2- -nitrobenzenesulfonamide A suspension of 29.4 g (98.0 mmol) of N'-Cyano -N- - (2-nitrophenylsulfonyl )-S-methylisothiourea in 100 ml of acetonitrile was treated with 6.2 ml (6.3 g, 0.20 mol) of anhydrous hydrazine. A mild exothermic reaction occurred as the reaction mixture became homogeneous. After stirring for 9 days the precipitated solid was collected by filtration and dried to afford 22.9 g of yellow solid. The crude product was recrystallized from HOAc to yield a total of 15.9 g (57 percent) of the desired product as a pale yellow solid, mp 255 2560C. IR and 1H NMR spectra were consistent with the assigned structure. Analysis: Calculated for C8H8N6O4S: C, 33.80; H, 2.84; N, 29.57; S, 11.28. Found: C, 34.11; H, 2.79; N, 29.35; S, 11.50. Example 3 N-(5,7-dimethyl-l,2,4-triazolo[1,5-aJ- pyrimidin-2-yl)-2-nitrobenzenesulfonamide A mixture of 2.43 g (9.00 mmol) of N-(5-amino -1, 2,4-triazol-3-yl )-2-nitrobenzenesulfonamide and 1.85 ml (1.80 g, 18.0 mmol) of 2,4 pentanedione in 25 ml of glacial acetic acid was heated at reflux for 19 hours. After cooling to room temperature, the solid which separated was collected by filtration, washed with acetic acid and dried in vacuo to yield 2.58 g (82 percent) of the desired product as an off-white crystalline solid, mp 255-2560C. IR and 1H NMR spectra were in agreement with the assigned structure. Analysis: Calculated for C13H12N6O4S: C, 44.83; H, 3.47; N, 24.13; S, 9.20. Found: C, 44.88; H, 3.34; N, 24.51; S, 9.09. Example 4 N'-Cyano-N-(2,5-dichlorophenylsulfonyl) -S-methylisothiourea A solution of 10.6 g (43.2 mmol) of 2,5-dichloro -benzenesulfonamide, 7.15 g (44.0 mmol) of 90 percent dimethyl N-cyanodithioiminocarbonate and 1.8 g (44 mmol) of NaOH in 60 ml of ethanol and 10 ml of H2 0 was heated at reflux for 6 hours. After cooling to room temperature the reaction mixture was poured into 600 ml of ice water. The resulting solution was acidified with 6N HCl to separate 2.2 g of the desired product as a white solid. Concentration of the filtrate gave an additional 8.5 g of the desired product. The total yield of material was 10.7 g (76 percent) of white solid, mp 145 C. IR and 1H NMR spectra were consistent with the assigned structure. Analysis: Calculated for CgH7C12N302S2: C, 33.34; H, 2.18; N, 12.96. Found: C, 33.50; H, 2.39; N, 12.82. Example 5 N-(5-Amino-1,2,4-triazol-3-yl)-2,5 -dichlorobenzenesulfonamide A mixture of 8.51 g (26.2 mmol) of N'-cyano-N -(2, 5-dichlorophenylsulfonyl )-S-methylisothiourea and 10 ml (10 g, 0.20 mol) of hydrazine monohydrate in 85 ml of ethanol was heated at reflux for 30 minutes. After cooling to room temperature, the solid which separated was collected and suspended in 170 ml of H20 and the suspension was acidified with concentrated aqueous HCl. After stirring the suspension for 4 hours the solid was collected and dried in vacuo to yield 5.10 g (57 percent) of the desired product as a hydrochloride salt, mp 306-3080C. IR and 1H NMR spectra were consistent with the assigned structure. Analysis: Calculated for C8H7Cl2N5O2S HCl: C, 27.88; H, 2.34; N, 20.32. Found: C, 28.36; H, 2.50; N, 19.78. Example 6 N-(5,7-dimethyl-1,2,4-triazolo[1,5-a]- -pyrimidin-2-yl)-2,5-dichlorobenzene -sulfonamide A solution of 4.60 g (13.3 mmol) of N-(5-amino -1,2,4-trizol-3-yl)-2,5-dichlorobenzenesulfonamide hydrochloride and 4.0 g (40 mmol) of 2,4-pentanedione in 60 ml of glacial acetic acid was heated at reflux for 4 hours. The reaction mixture was cooled to room temperature and poured into 500 ml of ice water to separate a solid. The solid was collected by filtration and dried to yield 4.53 g (92 percent) of the desired product as a white solid, m.p. 216,5 -218.5 C. Analysis: Calculated for C13H11Cl2N5O2S: C, 41.95; H, , 2.98; N, 18.81. Found: C, 41.83; H, 3.10; N, 18.67. Example 7 2-Chloro-N- ( 5-methyl-7-trifluoromethyl- -1,2,4-triazolo[1,5-a]pyrimidin-2-yl)- -benzenesulfonamide. A mixture of 2.19 g (8.00 mmol) of N-(5-amino -l,2,4-triazol-3-yl)-2-chlorobenzenesulfonamide and 1.09 ml (1.38 g, 8.96 mmol) of l,l,l-trifluoro-2,4-pentane -dione in 9 ml of glacial acetic acid was heated at reflux for 21 hours. After cooling to room temperature, the reaction mixture was poured into a mixture of ice and water. The solid which separated was collected by filtration, washed with water and dried to yield 2.90 g (93 percent) of the desired product as a white solid, mp 203-204.50C. IR and 1H NMR spectra were in agreement with the assigned structure. Analysis: Calculated for C13H9ClF3N5O2S: C, 39.86; H, 2.32; H, 17.88; Cl, 9.05; S, 8.18. Found: C, 40.23; H, 2.31; N, 18.22; Cl, 9.13; S, 8.26. Example 8 2-Chloro-N-(7-methyl-1,2,4-triazolo- -[1,5-a]pyrimidin-2-yl)benzenesulfonamide A sample of 3.0 ml (2.7 g, 20 mmol) of acetylacetaldehyde dimethylacetal was added to a solution of 2.74 g (10.0 mmol) of N-(5-amino-1,2,4-triazol-3-yl)-2 -chlorobenzenesulfonamide in 20 ml of glacial acetic acid at reflux over 12 hours. After the addition was complete the reaction mixture was heated at reflux for 15 hours and cooled to room temperature. The solid which separated was collected by filtration, washed with acetic acid and dried to yield 1.92 g (59 percent) of the desired product as white solid, mp 267.5-269"C. IR and 1H NMR spectra were in agreement with the assigned structure. Analysis: Calculated for C12H10C1N5O2 S: C, 44.52; H, 3.11; N, 21.63; Cl, 10.95; S, 9.90. Found: C, 44.36; H, 3.07; N, 21.69; Cl, 10.82; S, 10.15. Example 9 2-Chloro-N-(1,2,4-triazolo[1,5-a]- -pyrimidin-2-yl)benzenesulfonamide A mixture of 2.74 g (10.0 mmol) of N-(5-amino -1,2, 4-triazol-3-yl )-2-chlorobenzenesulfonamide and 3.3 ml (3.3g, 20 mmol) of malonaldehyde bis(dimethylacetal) in 10 ml of glacial acetic acid was heated at reflux for 24 hours. After cooling to room temperature, the solid which separated was collected by filtration, washed with acetic acid and dried to yield 1.78 g (58 percent) of the desired product as a tan solid, mp 253.5-256.50C. IR and 1H NMR spectra were in agreement with the assigned structure. Analysis: Calculated for CllH8ClN502S: C, 42.66; H, 2.60; N, 22.61; Cl, 11.45; S, 10.35. Found: C, 42.97; H, 2.60; N, 22.42; Cl, 11.19; S, 10.07. Example 10 2-Chloro-N-(6-Chloro-1,2,4-triazolo [1,5-a]pyridin-2-yl)benzenesulfonamide A mixture of 2.46 g (9.00 mmol) of N-(5-amino -1,2,4-trizol-3-yl)-2-chlorobenzenesulfonamide and 1.67 g (9.90 mmol) of mucochloric acid in 20 ml of DMF was heated to reflux for 16.5 hours. After cooling to room temperature, the solvent was removed by evaporation at reduced pressure and the residue was treated with 20 ml of 0.5 N NaOH. After stirring vigorously for - 30 minutes the mixture was filtered through celite and the filtrate was acidified with 2N HCl. The solid which separated was collected by filtration, washed with water and recrystallized from acetic acid - water to yield 0.70 g (23 percent) of the desired product as a light brown solid, mp 256.5-260.50C. IR and 1 H NMR spectra were in agreement with the assigned structure. Analysis: Calculated for C11H7C12N5O2S: C, 38.39; H, 2.05; N, 20.35; Cl, 20.60; S, 9.32. Found: C, 38.74; H, 2.08; N, 20.84; Cl, 19.54; S, 8.70. Example 11 2-Chloro-N-(6-methyl-1,2,4-triazolo (1,5-a] pyrimidin-2 -yl )benzenesul fonamide A mixture of 2.02 g (8.36 mmol) of 1,3-bis (dimethylamino)-2-methyltrimethinium perchlorate and 2.29 g (8.36 mmol) of N-(5-amino-1,2,4-triazol-3-yl)2-chlorobenzenesulfonamide in 25 ml of glacial acetic acid was heated at reflux for 19 hours. The solvent was removed by evaporation at reduced pressure, and the residue.was treated with 20 ml of 0.5N NaOH. Some additional 1N NaOH was added to dissolve all of the material ( pH 10). The solution was filtered and the filtrate was acidified with 2N HCl to precipitate a solid. The solid was collected by filtration, washed with water and dried to yield 2.34 g (87 percent) of the desired product as a pale yellow solid, mp 236-2390C. IR and 1H NMR spectra were in agreement with the assigned structure. Analysis: Calculated for C12H10C1N5O2S: C, 44.52; H, 3.11; N, 21.63; Cl, 10.95; S, 9.90. Found: C, 44.17; H, 3.05; N, 21.93; Cl, 11.01; S, 9.69. Example 12 N-(5-Amino-1,2,4-triazol-3-yl)-2,6- -dichlorobenzenesul fonami de. A mixture of 90.1 g (0.398 mol) of 2,6-dichlorobenzenesulfonamide, 64.7 g (0.398 mol) of dimethyl N-cyanodithioiminocarbonate and 58.3 g (0.420 mol) of powdered anhydrous K2CO3 in 800 ml of THF was heated at reflux for 3 hours. After cooling to 300C, 25.3 ml (25.6 g, 0.798 mol) of anhydrous hydrazine was added dropwise over 30 minutes. The resulting mixture was stirred for 3 days at ambient temperature and filtered. The solid collected was washed with THF, suspended in 400 ml of water and acidified with 180 ml of acetic acid. The resulting mixture was filtered, and the solid collected was washed with water and dried to yield 112 g (91 percent) of the desired product as a white solid, mp 3000C (decomp.) IR and 1H NMR spectra were in agreement with the assigned structure. Analysis: Calculated for C8H7Cl2N502S: C, 31.18; H, 2.29; N, 22.73; C1, 23.01; S, 10.40. Found: C, 31.39; H, 2.26; N, 22.70; Cl 22.88; S, 10.25. Following the above general procedures and employing appropriate starting materials the compounds indicated in the tables were prepared. TABLE I EMI16.1 Physical R1 R2 R3 R4 R5 Properties Elemental Composition C H N Cl S H H H H H mp 122 C Exact mass calcd. (decomp.) for C9H9N3O2S2: 255.0136 Found: 255.0125 NO2 H H H H mp 122 C Anal. Calcd. for C9H8N4O4S2: 36.00 2.69 18.66 -- 21.35 (decomp.) Found: 36.10 2.47 12.95 -- 21.22 CF3 H H H H mp 128 C Anal. (decomp.) Calcd. for C10H8F3N3O2S2: 37.15 2.49 13.00 -- 19.83 Found: 37.02 2.55 12.95 -- 20.00 Cl H H H H mp 126 C Anal. Calcd. for C9H8ClN3O2S2: 37:31 2:78 14:50 12:24 19:83 Found: 37.15 2.82 14.67 12.40 21.90 CH3 H H H H mp 129 C Exact mass calcd. (decomp.) for C10H11N3O2S2: 269.0292 Found: 269.0299 TABLE I(continued) Physical R1 R2 R3 R4 R5 Properties Elemental Composition C H N Cl S H H CH3 H H mp 137.5- Anal. Calcd. 139 C for C10H11N3O2S2: 44.59 4.12 15.60 -- - (decomp.) Found: 44.80 4.16 15.53 -- - H H Cl H H mp 140- Anal. Calcd. for C9H8ClN3O2S: 37.31 2.78 14.50 -- - 140.5 C (decomp.) Found: 37.50 2.97 14.68 -- - H H OCH3 H H mp 141,5 C Anal. Calcd. for C10H11N3O3S2: 42.09 3.89 14.73 -- - Found: 42.14 4.02 14.97 -- -i-Pr H i-Pr H i-Pr mp 165- Anal. Calcd. for C18H27N3O2S2: 56.66 7.13 11.01 -- - Found: 56.90 7.15 10.97 -- - Cl H H H Cl mp 239 C Anal. Calcd. 241 C for C9H7ClN3O2S2: 33.34 2.18 12.96 21.87 19.78 Found: 33.14 2.12 12.91 21.73 19.62 TABLE II EMI18.1 Physical R1 R2 R3 R4 R5 Properties Elemental Composition C H H Cl S H H H H H mp 293 C- Anal. Calcd. for C8H9N5O2S: 40.16 3.79 29.27 -- 13.40 294 C Found: 40.29 3.67 29.40 -- 13.26 CF3 H H H H mp 281 C- Anal. Calcd. for C9H8F3N5O2S: 35.18 2.62 22.79 -- 10.44 283 C Found: 35.01 2.57 22.91 -- 10.22 (decomp.) NO2 H H H H mp 255- Anal. Calcd. for C8H8N6O4S: 33.80 2.84 29.57 -- 11.28 256 C Found: 34.11 2.79 29.35 -- 11.50 Cl H H H H mp 307- Anal. Calcd. for C8H8CIN5O2S: 35.11 2.95 25.59 12.95 11.71 309 C Found: 34.84 2.90 25.56 13.03 11.56 (decomp.) CH3 H H H H mp 285- Anal. Calcd. for C9H11N5O2S: 42.68 4.38 27.65 -- 12.66 286 C Found: 42.59 4.17 27.79 -- 12.46 Physical R1 R2 R3 R4 R5 Properties Elemental Composition C H H Cl S H H CH3 H H mp 314- Anal. Calcd. for C9H11N5O2S: 42.68 4.38 27.65 -- - 315 C Found: 42.34 4.34 27.44 H H Cl H H mp 314- Anal. Calcd. for C8H8CIN5O2S: 35.11 2.95 25.59 -- - 315 C Found: 34.90 3.12 25.30 -- - (decomp.) H H OCH3 H H mp 300 C Anal. Calcd. for C9H11N5O3S: 40.14 4.12 26.01 -- - (decomp.) Found: 40.10 4.25 25.72 -- -i-Pr H i-Pr H i-Pr mp 314.5 C Anal. Calcd. for C17H27N5O2S: 55.86 7.45 19.16 -- - (decomp.) Found: 56.17 7.49 19.18 -- - Cl H H H Cl mp 295- Anal. Calcd. 296 C for C8H7Cl2N5O2S: 31.18 2.29 22.73 23.01 10.40 (decomp.) Found. 31.35 2.20 22.70 23.05 10.26 F H H H F mp 322- Anal. Calcd. for C8H7F2N5O2S: 34.91 2.56 25.45 -- - 323 C Found: 34.93 2.53 25.72 -- - (decomp.) Cl Cl H H H mp 326- Anal. Calcd. 327 C for C8H7Cl2N5O2S: 31.18 2.29 22.73 23.01 10.40 (decomp) Found: Table lll EMI20.1 R1 R2 R3 R4 R5 Properties Elemental Composition C H H Cl S CF3 H H H H mp 246.5- Anal. Calcd. 248 C for C14H12F3N5O2S: 45.28 3.26 18.86 -- 8.63 Found: 45.31 3.33 18.74 -- 8.71 CF3 H H H H mp 202.5- Anal. Calcd. for C14H15N5O2S: 52.98 4.76 22.07 -- 10.10 203.5 C Found: 52.43 4.56 21.78 -- 9.59 NO2 H H H H mp 255- Anal. Calcd. for C13H12N6O4S: 44.83 3.47 24.13 -- 9.20 256 C Found: 44.88 3.34 24.51 -- 9.09 (decomp.) Cl H H H H mp 216.5- Anal. Calcd. 219.5 C for C13H12CIN5O2S: 46.23 3.58 20.73 10.50 9.49 Found: H H H H H mp 241- Anal. Calcd. for C14H15N5O2S: 52.98 4.76 22.07 -- - 241.5 C Found: 52.70 4.96 22.06 -- - H H H H H mp 254- Anal. Calcd. 46.22 3.58 20.73 -- - 255.5 C for C13H12CIN5O2S: 46.10 3.75 20.69 -- - Found: Table lll(continued) Physical R1 R2 R3 R4 R5 Properties Elemental Composition C H H Cl S H H OCH3 H H mp 198.5- Anal. Calcd. for C14H15N5O3S: 50.44 4.54 21.01 -- - 199.5 C Found 50.43 4.70 20.29 -- -i-Pr H i-Pr H i-Pr mp 283 C Anal. Calcd. for C22H31N5O2S: 61.51 7.27 16.30 -- - (decomp.) Found: 61.30 7.33 16.28 -- - Cl H H H Cl mp 259- Anal. Calcd. 41.95 2.98 18.81 19.05 8.61 261 C for C13H11Cl2N5O2S: 41.86 2.94 19.09 18.09 8.39 Found: F H H H F mp 261- Anal. Calcd. 262 C for C13H11F2N5O2S: 46.02 3.27 20.64 -- - Found: 45.94 3.19 20.79 -- - Cl Cl H H H mp 231- Anal. Calcd 41.95 2.98 18.81 -- - Fond: 41.83 2.90 19.55 -- -- Table lV EMI22.1 Physical R1 R2 R3 R4 R5 Properties Elemental Composition C H H Cl S Cl H H Cl H mp 258.5- Anal. Calcd. 38.39 2.05 20.35 20.60 9.32 260.5 C for C11H7Cl2N5O2S: 38.74 2.08 20.84 19.54 8.70 Found: Cl H CH3 Cl CH3 mp 266- Anal. Calcd. 41.95 2.98 18.81 19.05 8.61 269 C for C13H11Cl2N5O2S: 42.51 3.03 18.98 18.16 8.41 Found: Cl H CF3 H CH3 mp 203- Anal. Calcd. 204.5 C for C13H9CIF3N5O2S: 39.86 2.32 17.88 9.05 8.18 Found: 40.23 2.31 18.22 9.13 8.26 Cl H CF3 H CF3 mp 224- Anal. Calcd. 226 C for C13H6CIF6N5O2S: 35.02 1.36 15.71 7.95 7.19 Found: 35.31 1.38 15.95 7.72 7.40 Cl H H CH3 H mp 236- Anal. Calcd. 239 C for C12H10CIN5O2S: 44.52 3.11 21.63 10.95 9.90 Found: 44.17 3.05 21.93 11.01 9.69 TABLE IV(continued) Physical R1 R2 R3 R4 R5 Properties Elemental Composition C H H Cl S Cl H CH3 CH3 CH3 mp 273- Anal. Calcd. 280 C for C14H14CIN5O2S: 47.80 4.01 19.91 10.08 9.11 Found: 47.78 3.90 20.19 10.20 9.17 Cl H CH2CH3 H CH2CH3 mp 216- for C15H16CIN5O2S: 49.25 4.41 19.14 9.69 8.76 218 C Found: 49.18 4.36 19.45 9.64 8.75 Cl H H H H mp 253.5- Anal. Calcd. 256 C for C11H8CIN5O2S: 42.66 2.60 22.61 11.45 10.35 Found: 42.97 2.60 22.42 11.19 10.07 Cl H CH3 H H mp 267.5- Anal. Calcd. 269 C forC12H10CIN5O2S: 44.52 3.11 21.63 10.95 9.90 Found: 44.36 3.07 21.69 10.82 10.15 Cl Cl CH3 Cl CH3 mp 296- Anal.Calcd. 297 C C13H10Cl3N502S: 38.39 2.48 17.22 -- - Found: 38.48 2.44 17.58 -- - Cl Cl H Cl H mp 262- Anal. Calcd. 264 C for C11H6Cl3N5O2S: 34.89 1.60 18.50 -- - Found: 34.72 1.78 19.12 -- - Cl Cl H H H mp 264- Anal. Calcd. 269 C for C11H7Cl2NOS: 38.38 2.05 20.35 20.61 9.32 Found: 38.29 2.05 20.08 19.80 9.13 TABLE IV (continued) Physical RÚ R5 X Y Z Properties Elemental Composition C H N Cl S Cl Cl CF3 H CF3 mp 238- Anal. Calcd. 240 C for C13H5F6N5O2S: 32.51 1.05 14.59 14.77 6.68 Found: 32.19 1.01 14.57 14.51 6.86 Cl Cl CH3 CH3 CH3 mp 347 C Anal. Calcd. (decomp.) for C14H13Cl2N5O2S: 43.53 3.39 18.13 18.35 8.30 Found: 43.52 3.29 18.42 18.37 8.29 Cl Cl CH2CH3 H CH2CH3 mp 259- Anal. Calcd. 261 C for C15H15Cl2N5O2S: 45.01 3.78 17.50 17.72 8.01 Found: 44.44 3.72 17.79 17.33 8.32 TABLE V EMI25.1 Physical RÚ Rê R Properties Elemental Composition C H N Cl S Br H H Cl mp 310 C Anal. Calcd. (decomp.) for C6H6ClN5O2S2: 25.76 2.16 25.04 12.68 22.93 - Found: 25.81 2.13 25.18 12.40 22.17 - H Br Br mp 325 C Anal. Calcd. (decomp.) for C6H5Br2N5O2S2: 17.88 1.25 17.38 -- 15.91 39.65 Found: 18.13 1.24 17.38 -- 15.07 37.71 TABLE VI EMI26.1 Physical RÚ Rê R X Z Properties Elemental Composition C H N Cl S Br H H Cl CH3 CH3 mp 310 C Anal. Calcd. (decomp.) for C11H10ClN5O2S2: 38.43 2.93 20.37 10.31 18.65 - Found: 38.08 2.83 20.47 8.59 18.91 - H Br Br CH3 CH3 mp 183- Anal. Calcd. 185 C for C11H9Br2N5O2S2: 28.28 1.94 14.99 -- 13.73 34.21 Found: 28.06 1.78 14.97 -- 13.90 33.60

Claims: 1. Process for making a compound having the formula EMI27.1 wherein Ar is an aromatic or heteroaromatic, substituted or unsubstituted ring system which comprises reacting a compound having the formula ArS02NH2 with dimethyl N-cyanodithioiminocarbonate in the presence of a base in a solvent. 2. Process of Claim 1 wherein the base is a tertiary amine or alkali metal hydroxide or alkoxide or an alkali metal carbonate. 3. Process of Claim 2 wherein the base is sodium hydroxide or potassium carbonate. 4. Process for making a compound having the formula EMI28.1 wherein Ar is an aromatic or heteroaromatic substituted or unsubstituted ring system which comprises reacting a compound having the formula EMI28.2 with an excess of hydrazine in the presence of a solvent 5. Process of Claim 4 wherein the solvent is acetonitrile, tetrahydrofuran, dimethylformamide or dimethylsulfoxide. 6. A compound having the formula EMI29.1 wherein R1 represents halo (F, Cl, Br, I), -NO2, phenyl, OAr, -CF3, -OCF3, -OCF2CF2H, -OCF2CCl2H, -OCH2CF3, -SCF3, -SCF2CF2H, -SCF2CCl2H, -SOCF3, -SOCF2CF2H, -SOCF2CCl2H, -SO2CF3, -SO2CF2CF2H, -SO2CF2CCl2H, -SR , -SOR6, -SO2R , -CN, -COOR7, -CONH2, -CINHR8, -CONR8(R9), -SO3R8 and -SO3CH2CF3; R2 and R4 represent H, halo (F, Cl, Br, I), C1-C4 alkyl, COOR7 and -OR8; R3 is H; and R5 represents H, C1 to C4 alkyl, halo (F, Cl, Br, I), NO2, CF3, -OCF3, -OCF2CF2H, -OCF2CCl2H, -OCH2CF3, -SCF3, -SCF2CF2H, -SCF2CCl2H, -SOCF3, -SOCF2CF2H, -SOCF2CCl2H, -SO2CF3, -SO2CF2CF2H, -SO2CF2CCl2H, -SR6, -SOR , -SO2R6, -CN, -COOR7, -CONH2, -CONHR8, -CONR8(R9), -SO3CH2CF3, -CR6R6OR6 and -CR6R6SR6 wherein Ar represents substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl, R6 represents H, aryl or C1-C4 alkyl, R7 represents C1-C6 alkyl, alkenyl,alkynyl, aryl, substituted alkyl or substituted aryl and R8 and R9 individually represent C1-C4 alkyl. 7. A compound having the formula EMI30.1 wherein Ar is an aromatic or heteroaromatic substituted or unsubstituted ring system. 8. Compound of Claim 7 wherein Ar is EMI30.2 wherein R1, R2, R3 R4 and R5 are as defined in Claim 6. 9. Compound of Claim 7 wherein Ar is EMI30.3 wherein RÚ, R2 and R3 are as defined in Claim 6.

Inventors: DUNBAR, JOSEPH E., KLESCHICK, WILLIAM A., VINOGRADOFF, ANNA P.
Applicants: THE DOW CHEMICAL COMPANY
Application year: 1986
Main classification: C07C157
IPC codes: C07D409, C07C67, A01N43, C07C325, B01J27, C07B61, B01J23, B01J31, C07C335, C07D487, C07D249, C07D333