THIOPHENESULFONYLUREA DERIVATIVES

Abstract: The present invention relates to novel thiophenesulfonylurea derivatives having a herbicidal activity, which is described in general formula (I), wherein P is P-1, P-2 or P-3 , wherein R is (1), (2), (3), wherein a is O or S; R<2> is C1-C6 alkyl substituted with 1 SIMILAR 3 halogens; R<4> and R<5> are respectively C1-C4 of alkyl; and R<6> and R<7> are respectively H, C1-C3 alkyl or C1-C3 haloalkyl; E is CH2 or single bond; R<3> is H or CH3; W is O or S; R1 and A defined in the claims, and these may be an agriculturally suitable salt.

Description: THIOPHENESULFONYLUREA DERIVATIVES TECHNICAL FIELD f The present invention relates to novel thiophenesulfonylurea derivatives having agriculturally suitable for herbicidal activity. BACKGROUND OF THE INVENTION 10 It is publicly well known that sulfonylurea derivatives have a herbicidal activity. Here are the formulas for the sulfonylureas. 1) U. S. Patent No. 4,370,480 discloses the compound having the following 15 formula wherein, R is H, alkyl, alkenyl, alkynyl or alkyl substituted with 1 ~ 4 of F, Cl, Br, OCH 3 , 20 CN or C0 2 R * , alkenyl substituted with 1 ~ 3 atoms of Cl, cycloalkyl, cycloalkenyl, cycloalkyl substituted with CH 3 , CH 2 CH 3 , Cl, OCH 3 , etc. or C0 2 R * ; X is H, Cl, CH 3 , OCH 3 , etc. ; Y is H, Cl, C j -Q of alkyl, halogen, alkoxy or alkyl substituted with CN, etc. ; 25 Z is CH. 2) U.S. Patent No. 4,786,314 discloses the compound having the following formula wherein, R 1 is alkyl, alkenyl, halogen, N0 2 , haloalkenyl, alkynyl, haloalkynyl, alkoxy, haloalkoxy, alkoxyalkyl, O I! R 2 is -CH-CN , -CH-SCN, -CH-PR 10 R" etc. ; R [ 16 R I 16 R I 16 R s is H, C r C 4 alkyl, alkenyl, alkynyl, C^CHaCl, C^CE^F, - alkyl substituted with OMe or SMe, or cycloalkyl. 3) U.S. Patent No. 4,612,035 discloses the compound having the following formula wherein, L is phenyl, naphthyl, pyridine or thiophene having substitutent ; R' is R 25 is H or alkyl ; R 26 is alkyl. 4) U. S. Patent No.4,659,369 discloses the compound having the following formula O O II II Q— S — NH — C— NH — A II o wherein, Q is Q-l, Q-2, Q-3 or Q-4 as followings. (Q-l) (Q-2) (Q-3) (Q-4) and then, R * is R 3 is H, C, -C 3 of alkyl or C r C 3 of alkoxy ; R 4 and R 5 are respectively -C, of alkyl; R 6 and R 7 are respectively H or C j -C^ of alkyl ; a is O, S or NCH 3 ; W j is O or s ; A is wherein, X 1 is CH 3 , OCH 3 , OEt or OCHF 2 ; Y 1 is O or CE^ ; Y 2 is H or CH 3 5) Japanes Patent Laid-Opened So 61-22083 discloses the compound having the following formula wherein, R is H or alkyl group ; X and Y are respectively methyl or methoxy group ; A is N or CH. As the above patents, many sulfonylurea herbicides have known until recently. Even with these herbicides, more and more weeds develop immunity forwards these herbicides and cause undesirable vegetations. Thus, continuous research is in demand to develop more effective and newer for a good harvest. Therefore, the object of the present invention is to provide new thiophenesulfonylurea derivatives having a very prominent herbicidal activity with a good selectivity for various vegetations and agriculturally suitable herbicides for treatment of pre-emergence and/or post-emergence or plant growth regulants. SUMMARY OF THE INVENTION The present invention relates to novel thiophenesulfonylurea derivatives having the following general formula (I) O W II II P— S — NH — C — N — A ( I ) II I O R 3 wherein, P is P-l, P-2 or P-3 as followings wherein, R 1 is H, C r C 3 alkyl, C,-Cj haloalkyl, halogen, CN, N0 2 , C r C 3 alkoxy, C,- C 3 haloalkoxy, SO^-R 11 , Cj- alkylthio, C j - alkylsulfinyl, C r C 3 alkylsulfonyl, SCHF 2 , NH 2 , NHCH 3 , N(Me) 2 , C j - alkyl substituted with Cj- alkoxy, C j - haloalkoxy, SH, SCH 3 , CN or OH ; or C0 2 R UI ; and then R 1 is H, C,-C 4 alkyl, C 2 -C 3 cyanoalkyl, methoxy or ethoxy ; R u is H, C r C 4 alkyl, C 3 -C 4 alkenyl, or when taken together connecting R 1 and R" , -(CH^-, -(CH^-, -(CH 2 ) 5 - or CH 2 CH 2 0CH 2 CH 2 -, may be formed ; R m is C,-C 4 alkyl, C 3 -C 4 alkenyl, C 3 -C 4 alkynyl, C,-C 4 alkyl substituted with 1 ~ 3 halogens or cyano groups, C 5 -C 6 cycloalkyl, - cycloalkylalkyl or C 2 -C 4 alkoxyalkyl ; Ris wherein, a is O or S ; R 2 is C,-C 6 alkyl substituted with 1 ~ 3 halogens ; R 4 and R 5 arc respectively C,-C 4 of alkyl; and R 6 and R 7 are respectively H, -C 3 alkyl or C J -C J haloalkyl ; E is CH 2 orsinglbond ; R 3 is H or CH 3 ; Wis O or S ; A is Al, A2, A3, A4, A5, A6 or A7 asfollowings ; Al A2 A3 A4 A5 A6 A7 wherein, Xis H, C r C 4 alkyl, C r C 4 alkoxy, C r C 4 haloalkoxy, C,-C 4 haloalkyl, C r C 4 haloalkylthio, C r C 4 alkylthio, halogen, C 2 -C 5 alkoxyalkyl, C 2 -C 5 alkoxyalkoxy, amino, C j -Q alkylamino, diC - alkyl) amino or C 3 -C 5 cycloalkyl ; Y is H, C r C 4 alkyl, C ,-C 4 alkoxy, C r C 4 haloalkoxy, C,-C 4 haloakylthio, C r C 4 alkylthio, C 2 - alkoxyalkyl, C 2 -C 5 alkoxyalkoxy, amino, Cj- alkylamino, d C j - alkyl)amino, C 3 -C 4 alkenyloxy, C 3 -C 4 alkynyloxy, C 2 -C '5 alkylthioalkyl, C C 4 haloalkyl, C 2 -C 4 alkynyl, azido, cyano, Cj- alkylsulfmylalkyl, C 2 - alkylsulfonylalkyl, OLOH, C 3 -C 5 cycloalkyl, O II C J -C J cycloalkoxy, C 2 -C j alkylthioalkoxy, -C-R 8 , CH, or -N-OCH, m is 2 or 3 ; L 1 and L 2 are independently O or S ; R 4 and R 5 are independently - alkyl ; R 8 is H or CH 3 ; Z is CH, N, CCH 3 or CG j H 5 ; Y * is O or CH 2 ; X 1 is CH 3 , OCH 3 , O I-L . or OCHF 2 ; Y 2 is CH 3 , CH 2 CH 3 , OCH 3 , OCH j C^, SCH 3 or SCH 2 CH 3 ; X is CH 3 , CH 2 CH 3 , or CH 2 CF 3 ; Y 3 is H or CH 3 ; X 3 is CH, or OCH Y 4 is CH 3 , OCH 3 , OC-,1 , CH 2 OCH 3 or Cl ; X 4 is CH 3 , OCH 3 , O H,, CH 2 OCH 3 or Cl ; and these may be an agriculturally suitable salt, and then, (1) if X is Cl, Br, F or I, Z is CH and Y is OCH 3 , OC^, NCH 3 (OCH 3 ), NH 2 , NHCH 3 , N(CH 3 ) 2 or OCHF 2 ; (2) if X or Y is OCHF 2 , Z is CH ; (3) X 4 and Y 4 are not Cl simultaneously ; (4) if W is S, R 3 is H, A is A v Z is CH or N and , Y is CH 3 , OCH 3 , OCH 2 CH 3 , CH 2 OCH 3 , C^, CF 3 , SCH,, OCH 2 CH=CH 2 , OCILC≡CH, OCH 2 CH 2 OCH 3 , CH(OCH 3 ) 2 or (5) if a number of total carbon atoms of X and Y is more than 4, a number of carbon atoms of R 2 is 4 or less than 4. DETAILED DESCRIPTION OF THE INVENTION Among the definitions according to the present invention, the following terms have the following meanings ; a) " Alkyl" used ether alone or in compound word such as "alkylthio" or "haloalkyl" etc. denotes straight chain or branched alkyls such as methyl, ethyl, n-propyl, isopropyl or buthyl isomers. b) "Alkoxy" denotes methoxy, ethoxy, n-propoxy, isopropoxy or buthoxy isomers. c) "Alkenyl" denotes straight chain or branched alkenes, for example, vinyl, 1- prophenyl, 2-prophenyl, or buthenyl, pentenyl, hexenyl or heptenyl isomers etc. d) "Alkynyl" denotes straight chain or branched alkynyl such as ethynyl, 1- propynyl, 2-propynyl, or buthynyl, pentynyl or hexynyl isomers. e) "Halogen" used ether alone or in compound ward "halo" denotes chlorine, fluorine, bromine or Iodine. A preferred group of thiophenesulfonylurea derivatives having the formula (1) shown as the below, in view of compounding of the polymer and herbicidal activity, wherein (1) R 3 is H ; W is O ; and E is singl bond ; (2) R 1 is H, F, C1, C,-C 2 alkyl, - haloalkyl, - alkoxy, - haloalkoxy, - alkylthio, O OOL, or CH j SCHa ; (3) X is CH 3 , OCH 3 , OCH 2 CH 3 , Cl, F, Br, OCHF 2 , CH 2 F, OCT^CHaF, OCH j CHF,, OαLCF,, CF 3 , CILC1 or CH j Br ; Y is H, C,- alkyl, OCH 3 , CH 2 OOl 3 , NHCH 3 , NCH j COCH j ), N(CH 3 ) 2 , CF 3 , SCH 3 , OCH 2 CH=CH 2 , OCH 2 C≡CH, CH C^, OCI^CHpCH,, CH j SCHa, OCHF 2 , SCHF 2 , cyclopropyl, C≡CH, or C≡ C-CH 3 ; (4) R 2 is CH^, CHF 2 , CHFCl, CH j Cl, CH j Br, CHFCH 3 , CI^CH- , CH 3 CH,α, CHC1CH 3 , CHC1 2 , CHFCH 2 F, CHClCH 2 α, CHFCH 2 C1, o r CF(CH 3 ) 2 ; (5) A is A j ; X is CH 3 ,OCH 3 , OCH 2 CH 3 , Cl or OCHF 2 ; Y is CH 3 , H,, OCH 3 , ^OCH,, CH(OCH 3 ) 2 , OCHF 2 , NHCH 3 , N(Me) 2 or cyclopropyl, and R 1 is H, CH 3 or OCE^. The novel compounds having the above formula(I) according to the present invention have a very strong herbicide activity and good selectivity for a useful vegetation. The compounds of the present invention can be prepared by reactions as described in herein below. The compounds of general formula(I) can be obtained by reacting the compounds having the following formula(II) with an amine compound of the following formula(III). (Method 1 ) ( II ) ( III ) wherein, The above reaction may be carried out in solvent such as methylenechloride, dichloro ethane or chloroform, and then the solvent can be used with catalystic amount of base such as DABCO(l,4-diazabicyclo[5.4.0]undece-7-ene), DBU(1,8- diazabicycIo[5.4.0]undece-7-ene), etc. The compounds of general formula(I) can be obtained by reacting the compounds having the following formula(IV) with a carbamate compound of the following formuIa(V). (Method 2) ( IV ) ( V ) The compounds of the above formula(II) can be manufactured by reacting sulfonamide with phosgene. (Method 3) OjNCC The thiophenesulfonamide compounds of the above formula(TV) may be prepared by the following reaction process. (Method 4) 1. n-BuLi, -78t 2. R -C-L, -100 * C ( IV - a ) ι o In the above reaction, L is leaving group such as OEt, NMe 2 or N(CH 3 )OCH 3 and R, R 1 and R 2 are as the above defined. Sulfonamide substituted at 2,3-position of the following formula(TV-b) can be obtained by the method 4 of the above, but 2,3-dibromothiophene is used as the 15 starting material. (Method 5) ( IV - b ) Sulfonamide of the following formula(IV-c) can be obtained by the following reaction process, and then 3-bromothiophene is used as the starting material. (Method 6) * uC 'SOJNIHj ( IV - c ) The heterocyclic amine compound of formuIa(m) may be prepared by a skill person in this technical field from a method disclosed in literatures or the i o simple transformation of it. For example, European Patent Application No. 84,244 (Pub. July 27, 1983) and J. Am. Chem. Soc., 69,3072(1947) of W. Braker et al. discloses a method for preparing aminopyrimϊdine and triazine substituted with acetyl group. European Patent No. 72,347 and U. S. Patent No.4,443, 243/4, 487, 915 disclose a method for 5 preparing aminopyrimidine and or triazine substituted with haloalkyl such as OCHF 2 , SCHF 2 , OCH j CH j F and OCILCF,, etc. and haloalkylthio as a substitution group. European Patent No. 108,708, U.S.Patent No. 4,515,626/4,600,428 disclose cyclopropylpyrimidine and/or triazine substituted with alkyl, haloalkyl, alkoxy, 0 haloalkoxy, alkylamino, dialkylamio and alkoxyalkyl group etc. European Patent No. 15,863 discloses a method for preparing the compound of the above formula(VI), as 5,6-dihydro-puro[2,3-d] pyrmidine-2- amine compounds and cyclopenta[d]pyrimidine-2-amine compounds which A is A 2 ; and 6,7-dihydro-5H-pyrano-[2,3-d] pyrimidine-2-amine compound which A is A 3 . European Patent No. 46,677 discloses puro[2,3-d]pyridine-2-amine compounds which A is A 4 in the formula(VI), and European Patent No. 73,562 5 discloses heterocyclic compounds which A is A 5 . The compound of formula(VI) which A is A 6 can be prepared by European Patent No. 94,260. The compound of formula(VI) which A is A 7 can be manufactured by the method of European Patent No. 125,864. Common methods for preparing aminopyridine and triazine compounds are ι o arranged on the following literatures : " The chemistry and Heterocyclic compounds", Series, Literscience Publishers, Inc., New York and London ; " Pyrimidines" , Vol. 16, DJ. Brown Ed. ; "S-Triazines and Derivatives", Vol. 13, E.M. Smolin and L. Rapapor Composition of triazine compounds is disclosed in F.C. Schaefer, U.S.Patent No. 3,154,547 and K.R. 5 Huffman and F.C. Schaefer, J. Org. Chem., 28, 1812(1963). On the other hand, salts of the compound of the above formula also are useful as herbicide, and they can be prepared by various methods according to prior art. For example, metal salts of the compound can be prepared by reacting the 0 above formula(I) compound with strong basic anion, e.g. alkali or alkaline earth metal solution having hydroxyl group, alkoxide or carbonate, and also quaternary amine salt alike. A salt of the formula(I) compound may also be obtained by cation exchange. The cation exchange can be manfacturcd by directly reacting solution 5 containing cation for exchange with solution of salt of formula(I), for example, solution of alkali metal or quaternary amine salt. This method is useful when the desired salt is water insoluble, for example, copper salt is separarated by filtering. This ion exchange may be carried out by passing through a column of cation exchange resin with solution of salt of the formula®, for example, alkaline metal or quartermary amine salt solution. This method is useful when the desirable salt is water soluble, especially sodium, potassium or calcium salt. The above manufacturing methods are summarized briefly, but the methods can be easily carried out by a skill person in this technical field of composition and manufacturing for sulfonyl urea or organic composition. The compounds of the above general formula(I) according to the present invention specify as the following Tables 1 ~ 45 ; Table 1. R 1 R 2 R 3 pCC) R 1 R 2 R 3 X mpC R 1 R 2 X mp(°C) R 1 R 2 mp(°C) R 1 R 2 R 3 m P (°C) R 1 R 2 R 3 mp(°C) Table 2. R> R 3 X mpCC) R 1 R 2 R 3 X mp(°Q R 2 R 3 mp(°C) R 1 R 2 R 3 p(°C) R 1 R 3 X mp(°C) R 3 pCQ R 1 R 2 R 3 X mp(°C) Table 3. R 1 R 2 R 3 mp(°C) 33 R 1 R 2 R 3 X mpfC) R 1 R 2 R 3 mpCC) Table 4. R 1 R 2 R 3 X mpOQ 37 2/16525 R 1 R 2 R 3 m Q Table 6. R 1 R 3 X mp Table 7. R 1 R 2 R 3 X 1 Y 1 mp 41 Table 8. R 1 R 2 R 3 X 1 Y 1 mp Table 9. R l R 2 R 3 mp Table 10. R 1 R 2 R 3 X 1 Y l mp Table 11. R 1 R 2 R s X 1 mp Table 12. R 1 R 2 R 3 X 1 mp Table 13. Table 14. 48 Table 15. Table 16. R 1 R 2 R 3 X 2 mp Table 17. Table 18. R 2 R 3 X s Y 2 mp 52 Table 19. R 1 R 2 R 3 X 3 mp Table 20. R 2 R 3 X 3 mp Table 21. Table 22. R 1 R 2 R 3 X 4 Y Z 1 mp 56 Table 23. R 1 R 3 X 4 Y 4 mp Table 24. R 1 mp 58 Table 25. Table 26. R- R 2 W mp 60 Table 27. R 2 R 3 W mp Table 28. pCC) R 1 R 2 R 3 mpCC) 66 Table 29. R 1 R 2 R 3 X mpCC) R 2 mpCC) Table 30. R 1 R 2 mpCQ R 2 R 3 pCQ Table 31. R» R 2 mpCQ R 1 R 2 mp Q 75 Table 32. R 2 R 3 mp(°Q Table 33. R 2 R 3 mpCQ Table 34. R 1 mp("C) R 2 R 3 mpCC) R 1 R 3 X mpCC) 84 Table 35. R 3 mpCQ R 2 mpCQ Table 36. R 1 R 2 R 3 X mpfC) Ncαy Table 37. R 1 R 2 mpCQ R 2 R 3 mpCQ Table 38. R 1 R 2 R 3 mpCQ 92 Table 39. R 2 mpCQ Table 40. Table 41. R 1 R 2 mpCQ R l R 2 mp(°C) Table 42. R l R 2 R 3 mp(°C) Table 43. R 1 R 2 R 3 mpCQ R 1 mp(°C) R 1 R 2 R 3 mp(°C) Table 45. R 1 R 3 rnpTQ R 1 R 2 R 3 mpCQ Test results indicate that the compounds of the present invention are highly active pre-emergent or post-emergent herbicides or plant growth regulants. Many of them have utility for broad-spectrum pre- and/or post-emergency weed control in areas where complete control of all vegetation is desired, such as around fuel storage tanks, ammunition depots, industrial storage areas, parking lots, drive-in theaters, around billboards, highway and railroad structures. Some of the compounds have utility for selective weed control in crops such as wheat and barley. Alternatively, the subject compounds are useful to modify plant growth. The rates of application for the compounds of the present invention arc determined by a number of factors, including their use as plant growth modifiers or as herbicides, the crop species involved, the types of weeds to be controlled, weather and climate, formulations selected, mode of application, amount of foliage present, etc. In general terms, the subject compounds should be applied at levels of around 0.05 to 10 kg/ha, the lower rates being suggested for use on lighter soils and/ or those having a low organic matter content, for plant growth modifications or for situations where only short-term persistence is required. Formulations Useful formulations of the compounds of formula(I) can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, weftable powders, emulsifiable concentrates and the like. Many of these may be applied directly. Sprayable formulations can be extented in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain about 0.1% to 99% by weight of active ingredient(s) and at least one of (1) about 0.1% to 20% surfactant(s) and (2) about 1% to 99.9% solid or liquid inert diluent(s). More specially, they will contain these ingredients in the following approximate proportions * Active ingredient plus at least one of a surfactant or a diluent equals 100 weight percent. Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactants to activate ingredient are sometimes desirable, and are achieved by incorporation into the formation or by tank mixing. Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., DorlandΦooks, Caldwell, N.J., but other solids, either mined or monufacturcd, may be used. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvent Guide", 2nd Ed., Interscience, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates ; Solution concentrates are preferably stable against phase separation at O l . "McCutcheon's Detergents * and Emulsifiers Annual", MC Publishing Corp., Ridgewood, N.J., as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., New York, 1964, list surfactants and recommended uses. AH formulations can contain minor amounts of additives to reduce foaming, caking, corrosion, microbiological growth, etc. The methods of making such compositions are well known. Solutions arc prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Patent No. 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J.E. Browning, "Agglomeration", Chemical Engineering, Dec.4, 1967, pp, 147ff. and "Perry's chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-57ff. For further information regarding the art of formulation, see for example : H.M. Loux, U.S.Patent. No. 3,235,361, Feb. 15,1966, Col. 6, tine 16 through Col. 7, line 19 and Examples 10 through 41 ; R.W. Luckenbaugh, U.S.Patent. No. 3,309,192, Mar. 14, 1967, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182 ; H. Gysin andE. Knusli, U.S.Patent No.2,891,855, June 23, 1959, Col. 3, line 66 through Col. 5, line 17 and Examples 1 - 4 ; G.CKIingman, "Weed Control as a Science", John Wiley and S.A. Evans, "Weed control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pp. 101-103. The compounds of the present invention can be used independently and may be used in combination with any other commercial herbicide. A summary of the possible combination herbicides is given below EXAMPLE 1 : 3-Bromo-4-fluoroacetylthiophene 3,4-dϊbromothiophene(10g, 0.041 mol) was dissolved in anhydrous edier and the solution was cooled to -78 * C under nitrogen atmosphere, and herein 17ml of 2.5N n-butyl lithium was added dropwise. The solution stirred for lOhr at -78 " C was cooled to -100 " C, and herein ethyl fluoroacetate(4.8πzZ, 0.05 mol) was added dropwise. After stirring for 40min, an excess of saturated solution of ammonium chloride was added and stirred. The temperature of the reaction mixture was raised to room temperature, and herein an excess of ether was added to separate organic layer. The organic layer was dried with magnesium sulfate, filtered and concentrated, and then the obtained residue was chromatographed through silica gel using 2 : 1 solution of methylene chloride/hexane to afford 6g of the desired product, (white solid, yield : 65%) m.p. : 76 - 77 * C Η NMR ( CDC1 3 ) δ 5.40(d, 2H, J=48Hz), 7.42(d, 1H, J=4Hz), 8.37(d, 1H, J=4Hz) EXAMPLE 2 : 3-(2-Fluoromethyl-l,3-dioxalan-2-yl)-4-bromothiophene 3-bromo-4-fluoroacetylthiophene(10g, 0.045 mol) was added in ethylene glycol, and herein trimethyl silan chloride (22.7ml, 0.18 mol) was added under stirring. After stirring for 12hr, the solution was poured in an excess of saturated solution of sodium bicarbonate and stirred, and then an excess of ether was added and shaked to separate ether layer. The ether layer was dried with magnesium sulfate, filtered and concentrated to afford 10.4g of the desired product, (light borwn liquid, yield : 87%). Η NMR ( CDCI 3 ) S 4. l(m, 4H), 4.7(d, 2H, J= 8Hz), 7.4(d, 1H, J=4Hz), 7.6(d, 1H, J=4Hz) EXAMPLE 3 : 3-(2-Fluoromethyl- l ,3-dioxalan-2-yl)-4-thiophene- sulfonamide 3-(2-fluoromethyl-l,3-dioxalan-2-yl)-4-bromothiophene (19g, 0.07 mol) was dissolved in anhydrous ether and the solution was cooled to -78 "C under nitrogen atmosphere, and herein n-butyl lithium (31ml, 0.08 mol) was added dropwise. After stirring for lOmin at -78 " C , an excess of sulfurous acid gas was added, and then the solution was stirred for 30min at -781; . The temperature of the reaction mixture was raised to room temperature, and the solution was filtered. The obtained white solid was washed with ether, dried and dissolved in solution mixed 40ml of water with 40ml of isopropyl alcohol, and then the solution was cooled to 0X2.. After adding portionwise N-chlorosuccinimide (11.4g, 0.085 mol), the solution was stirred for 2hr at room temperature, and filtered to obtain a white solid. The white solid was washed with water and dissolved in ethylacetate solution, and herein an excess of aqueous ammonia was added. After stirring for lhr, the reacting solution was concentrated, and then the obtained solid was washed with a small quantity of ether to afford 13g of the desired product (light yellow solid, yield : 68%). m.p. : 126 - 130 * C Η NMR ( CDCI 3 + DMSO-d 6 ) £ 4.2(m, 4H), 4.86(d, 2H, J=48Hz), 6.6(brs, 2H), 7.85(d, 2H, J=4Hz), 8.3(d, 2H, J=4Hz) IR(KBr) : ^ (NH 2 ) 3350, 3250 cm "1 EXAMPLE 4 : 3-(2-Fluoromethyl-l,3-dioxalan-2-yl)-N-[(4-methoxy-6- methyltriazin-2-yl)aminocarbonyl] -4-thiophene- sulfonamide 5 3-(2-fluoromethyl-l,3-dioxalan-2-yl)-4-thiophenesulfonamide (lg, 0.0037 mol) was dissolved in 20ml of acetonitrile and phenyl (4-methoxy-6-methyltriazin- 2-yl) carbamate (0.86g, 0.0037mol) was added at room temperature, and herein 0.8 ml of DBU was added dropwise. After stirring for 1 hr, the reacting solution was diluted with 100ml of i o methylene chloride, and was washed with hydrochloric acid solution. The organic layer was dried with magnesium sulfate, filtered and concentrated. The obtained solid was washed with a small quantity of ether to afford 1.3g of the desired product (yield : 84%). m.p. : 212 - 214 * 0 5 Η NMR ( DMSO-d δ 2.51(s, 3H), 3.7 - 4.1(m, 4H), 4.05(s, 3H), 4.7(d, 2H, J=48Hz), 7.8(d, 2H, J=4Hz), 8.5(d, 2H, J=4Hz), ll.l(brs, 1H), 12.5(brs, 1H) IR(KBr) : v (C=0) 1720 cm 1 0 EXAMPLE 5 : 3-Bromo-2-fluoroacetylthiophene 2,3-dibromothiophene (lOg, 0.041mol) was dissolved in anhydrous ether and cooled to -78 "C under mtrogen atmosphere, and herein 17ml of 2.5N n-butyl lithium was added dropwise. After stirring for lOmin at -78 "C , the temperature of the reacting solution was cooled to -100 * C, and herein ethylfluoro acetate(4.8ώ, 0.5mol) was added dropwise. After stirring for 40min, an excess of saturated solution of ammonium chloride .was added and stirred, and after raising the temperature to room temperature, an excess of ether was added to separate organic layer. The obtained orginic layer was dried with magnesium sulfate, filtered and concentrated. The residue was chromatographed through silica gel using 2 : 1 solution of methylene chloride and hexane to afford 6g of the desired product (white solid, yield : 65%). Η NMR ^DO,)* 5.6(d, 2H, J=48Hz), 7.25(d, 1H, J=5Hz), 7.75(d, 1H, J=5Hz) EXAMPLE 6 : 2-(2-Fluoromethyl-l,3-dioxalan-2-yl)-3-bromothiophene 3-bromo-2-fluoroacetylthiophene (lOg, 0.045 mol) was dissolved in ethylene glycol, and trimethylsilane chloride (22.7ml, 0.18 mol) was added under stirring. After stimng for 12hr, the solution was poured in an excess of saturated solution of sodium bicarbonate and stirred, and herein an excess of ether was added and stirred to separate ether layer. The obtained ether layer was dried with magnesium sulfate, filtered and concentrated to afford 1 lg of the desired product (light brown liquid, yield : 92%). 'H NMR (CDCl 3 ) δ 4.1(m, 4H), 4.7(d, 2H, J=48Hz), 6.95(d, 1H, J=5Hz), 7.2(d, 1H, J=5Hz) EXAMPLE 7 : 2-(2-Fluoromethyl-l,3-dioxalan-2-yl)-3-thiophenesulfonamide 2-(2-fluoromethyl-l,3-dioxalan-2-y;)-3-bromothiophene(19g, 0.07 mol) was dissolved in anhydrous ether and the solution was cooled to -78 " C , and herein n- butyl lithium (31 ml, 0.08mol) was added dropwise under nitrogen atmosphere. After stirring for lOhr at -78 X2 , an excess of sulfurous acid gas was added, and after stirring 30hr at -78 "C , the temperature of the reacting solution to filter the solid material. The solid was dried and dissolved in solution mixed 40ml of water with 40 ml of isopropyl alcohol, and after cooling to CC , herein N-chlorosuccinimide (11.4g, 0.085 mol) was added portionwise. After stirring for 2hr at room temperature and filtering, the obtained solid was washed with water and dissolved in ethyl acetate solution, and herein an excess of aqueous ammonia was added while stirring for lhr at room temperature. The reacted solution was concentrated, and then the obtained solid was washed with a small quantity of ether to afford 14g of the desired product (yield : 74%). m.p. : 120 - 121 "C Η NMR ( CDCl 3 + DMSO-d 6 ) δ 4.1(m, 4H), 4.75(d, 2H, J=48Hz), 6.7(brs, 2H), 7.4(s, 2H) IR(KBr) : v (NH 2 ) 3380, 3270 cm '1 EXAMPLE 8 : 2-(2-FIuoro-methyl-l,3-dioxalan-2-yl)-N-[(4-methoxy-6- methyltriazin-2-yl) aminocarbonyl]-3-thiophenesulfonamide 2-(2-fluoromethyl-l,3-dioxalan-2-yl)-3-thiophenesulfonamide (lg, 0.0037 mol) was dissolved in 20ml of acetonitrile and phenyl(4-methoxy-6-methyltriazin-2- yl) carbamate (0.86g, 0.0037mol) was added at room temperature, and herein 0.80 ml of DBU was added dropwise. After stirring for lhr, the solution was diluted with 100ml of methylene chloride, and was washed with 5% hydrochloric acid solution. The separated organic layer was dried with magnesium sulfate, filtered and concentrated, and then the obtained solid was washed with hexane or a small quantity of ether to afford 1.34g of the desired product (yield : 87%). m.p. : 186 - 189 * C Η NMR ( DMSO-dg) δ 2.55(s, 3H), 4.0(m, 4H), 4.85(d, 2H, J=48Hz), 7.6(q, 2H), 10.9(brs, 1H) IR(KBr) : v (C=0) 1700 cm" 1 EXAMPLE 9 : 3-Fluoroacetylthiophene 3-bromothiophene(10g, 0.061 mol) was dissolved in anhydrous ether and the solution was cooled to -7813 under nitrogen atmosphere, and herein 27 l of 5 2.5N n-butyl lithium was added dropwise. After stirring for lOmin at -78 " C , the temperature of the solution was cooled to -100 , and herein ethylfluoroacetate (7.1ml, 0.074 mol) was added dropwise. The solution was stirred for 40min, and an excess of saturated solution of ammonium chloride was added. l o After raising to room temperature, the reaction mixture was extracted with an excess of ether. The obtained residue was dried with magnesium sulfate, filtered and concentrated, and then chromatographed throngh silica gel using 2 : 1 solution of methylenechloride/hexane to afford 6.4g of the desired product (yield : 72%). 15 Η NMR ( CDCI 3 ) δ 5.48(d, 2H, J=48Hz), 7.35 - 8.4(m, 3H) EXAMPLE 10 : 3-(2-Fluoromethyl-l,3-dioxalan-2-yl)thioρhene 3-fluoroacetylthiophene (lOg, 0.069 mol) was dissolved in ethylene glycol, and herein trimethylsilane chloride (35ml, 0.275 mol) was added under stirring. 0 After stirring for 12hr, the solution is poured in saturated solution of sodium bicarbonate and stirred. The reaction mixture was extracted with an excess of ether, and then the obtained residue was dried with magnesium sulfate, filtered and concentrated to afford 1 lg of the desired product (yield : 85%). 5 Η NMR ( CDCI 3 ) δ 4.0(m, 4H), 4.44(d, 2H, J=48Hz), 7:0 - 7.5(m, 3H) EXAMPLE 11 : 3-(2-Fluoromethyl-l,3-dioxalan-2-yl)-2-thiophenesulfonamide 3-(2-fluoromethyl-l,3-dioxalan-2-yl)thiophene (5g, 0.026mol) was dissolved in anhydrous ether, and herein 12nzZ of n-butyl lithium was added dropwise under nitrogen atmosphere. After stirring for lhr at room temperature, the temperature of the solution was raised in order to reflux for 30min, and the solution was cooled to -7813 and sulfurous acid gas was added. The reacting solution was stirred for 30min at -7813 , and the temperature was raised to room temperature. The obtained solid was filtered, dried and dissolved in solution mixed 20ml of water with 20ml of isopropyl alcohol, and after cooling to 013, N-chlorosuccinimide (3.9g, 0.029 mol) was added portionwise. After stirring for 2hr at room temperature, the obtained solid was filterd, washed with water and was dissolved in ethyl acetate, and herein an excess of aqueous ammonia was added. After stirring for lhr at room temperature, the reaction mixture was concentrated, and then the obtained solid was washed with a small quantity of ether to afford 2g of the desired product (yield : 92%). Η NMR ( CDCl 3 +DMSO-d 6 ) δ 4.1(m, 4H), 4.65(d, 2H, J=48Hz), 6.7(brs, 2H), 7.1(d, lH, J=5Hz), 7.4(d, 1H, J=5Hz). EXAMPLE 12 : 3-(2-Fluoromethyl-l,3-dioxalan-2-yl)-N-[(4-methoxy-6- methyltriazin-2-yl)aminocarbonyl]-2-thiophenesulfonamide 3-(2-fluoromethyl-l,3-dioxalan-2-yl)-2-thiophenesulfonamide (lg, 0.0037 mol) was dissolved in 20ml of acetonitrile and phenyl(4-methoxy-6-methyltriazin-2- yl)-carbamate (0.86g, 0.0037 mol) was added at room temperature, and herein 0.8 ml of DBU was added dropwise. After stirring for lhr, the solution was diluted with methylene chloride, and was washed with 5% hydrochloic acid solution. The separated organic layer was dried with magnesium sulfate, filtered and concentrated, and then the obtained solid was washed with hexane and ether to afford 1.3g of the desired product (yield : 84%). m.p. : 167 - 17013 Η NMR ( DMSO-d δ 2.55(s, 3H), 4.0(m, 4H), 4.7(d, 2H, J=48Hz), 7.3(d, 1H, J=5Hz), 7.8(d, 1H, J=5Hz), 10.9(brs, 1H) 5 IR(KBr) : * ^ (C=0) 1700 cm *1 EXAMPLE 13 : 4-(l, l-Diethoxy-2-fluoroethyl)-N-[(4-methoxy-6-methyl- pyrimidin-2-yl)aminocarbonyl]-3-thiophenesulfonamide 4-(l, l-diethoxy-2-fluoroethyl)-3-thiophensulfonamide (lg, 0.0034 mol) was 10 dissolved in 20ml of acetonitrile, and phenyl(4-methoxy-6-methylprimidin-2-yl) carbamate(0.87g, 0.0034mol) was added at room temperature, and herein O.Sml of DBU was added dropwise. After stirring for lhr, the solution was diluted with lOOraZ of methylene chloride, and washed with 5% hydrochloric acid solution. The residue was dried 15 with magnesium sulfate, filtered and concentrated, and then the obtained solid was washed with hexane and ether to afford 1.2g of the desired product, m.p. : 145 - 14813 IR(KBr) : t> (C=0) 1710 cm "1 :c EXAMPLE 14 : 3-(2-Fluoromethyl-l ,3-dioxalan-2-yl)-N-[(4-methoxy-6- methylprimidin-2-yl)aminocarbonyl)-4- thiophenesulfonamide 3-(2-fluorommethyl- 1 ,3-dioxalan-2-yl 4-thiophenesulfonamide (lg, 0.0037 mol) was- dissolved in 20ml of acetonitrile and phenyl (4-methoxy-6- methylpyrimidin-2-yl)carbamate (0.86g, 0.0037 mol) was added at room 5 temperature, and herein &mL of DBU was added dropwise. After stirring for lhr, the solution was diluted with 100ml of methylene chloride, and was washed with 5% hydrochloric acid solution. The separated organic layer was dried with magnesium sulfate, filtered and concentrated, and then the obtained solid was washed with hexane and ether to afford 1.3g of the desired product (yield : 84%). m.p. : 185 - 18913 IR(KBr) : v (C=0) 1709 cm '1 5 EXAMPLE 15 : Wettable Powder 3-(2-FIuoromethyl-l,3-dioxalan-2-yl)-N-[(4-methoxy-6-methyltriazin-2- yl)aminocarbonyl]-4-thiophenesulfonamide 80% sodium alkylnaphthalenesulfonate 2% l o sodium ligninsulfonate 2% synthetic amorphous silica 3% kaolinite 13% The ingredients are blended, hammer-milled until all the solids are essentially under 50 microns, reblended, and packaged. 5 EXAMPLE 16 : Wettable Powder 3-(2-FIuoromethyI-I,3-dioxalan-2-yl)-N-[(4-methoxy-6-methyltriazin-2- yl)aminocarbonyl]-4-thiophenesulfonamide 50% sodium alkylnaphthalenesulfonate 2% 0 low viscosity methyl cellulose 2% diatomaceous earth 46% The ingredients are blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in diameter. The product is reblended before packaging. EXAMPLE 17 : Granule wettable powder of Example 16 5 % attapulgite granules(U.S.S. 20-40 mesh ; 0.84 - 0.42 mm) 95% A sluπy of wettable powder containing 25% solids is sprayed on the surface of attapulgite granules in a double-cone blender. The granules are dried and packaged. EXAMPLE 18 : Extruded Pellet 3-(2-Fluoromethyl- 1 ,3-dioxalan-2-yl)-N-[(4-methoxy-6-methyltriazin-2- yl)aminocarbonyl]-4-thiophenesulfonamide 25% anhydrous sodium sulfate 10% crude calcium lignisulfonate 5% sodium alkylnaphthalenesulfonate 1% calcium/magnesium bentonite 59% The ingredients are blended, hammer-milled and then moistened with about 12% water. The mixture is extruded as cylinders about 3 mm diameter which are cut to produce pellets about 3mm long. They may be used directly after drying, or the dried pellets may be crushed to pass a U.S.S. No. 20 sieve(0.84 mm openings). The granules held on a U.S.S. No. 40 sieve(0.42 mm openings) may be packaged for use and the fines recycled. EXAMPLE 19 : Oil Suspension 3-(2-Fluoromethyl- 1 ,3-dioxalan-2-yl)-N-[(4-methoxy-6-methyltriazin-2- yl)aminocarbonyl]-4-thiophenesulfonamide 25% polyoxyethylene sorbitol hexaoleate 5% highly aliphatic hydrocarbon oil 70% The ingredients are ground together in sand mill until the solid particles have been reduced to under about 5 microns. The resulting thick suspension may be applied directly, but preferably after being extended with oils or emulsified in water. EXAMPLE 20 : Wetting Powder 3-(2-Huoromethyl- 1 ,3-dioxalan-2-yl)-N-[(4-methoxy-6-methyltriazin-2- yl)aminocarbonyl]-4-thiophenesulfonamide 20% 5 sodium alkylnaphthalenesulfonate 4% sodium Iigninsulfonate 4% low viscosity methyl cellulose 3% attapulgite 69% The ingredients are thoroughly blended. After grinding in a hammer-mill i o to produce particles essentially all below 100 microns, the material is reblended and sifted through a U.S.S. No. 50 sieve(0.3 mm openings) and packaged. EXAMPLE 21 : Low Strength Granule 3-(2-Fluoromethyl- 1 ,3-dioxalan-2-yl)-N-[(4-methoxy-6-methyltriazin-2- 5 yl)aminocarbonyl]-4-thiophenesulfonamide 1% N,N-dimethylformamide 9% attapulgite granule (U.S.S.20-40 sieve) 90% The active ingredient is dissolved in the solvent and the solution is sprayed upon dedusted granules in a double cone blender. 0 After spraying of the solution has been completed, the blender is allowed to run for a short period and then the granules are packaged. EXAMPLE 22 : Aqueous Suspension 3-(2-Fluoromethyl-l,3-dioxalan-2-yl)-N-[(4-methoxy-6-melhyltriazin-2- yl)aminocarbonyI]-4-thiophenesulfonamide 40% polyacrylic acid thickener 0.3% dodecylphenol polyethylen glycol ether 0.5% disodium phosphate 1% monosodium phosphate 0.5% polyvinyl alcohol 1% water 56.7% The ingredients are blended and ground together in a sand mill to produce particles essentially all under 5 microns in size. EXAMPLE ' 23 : Solution ammonium salt of N-[(4,6-dimethoxytriazin-2-yl)aminocarbonyl]-3- (2-fluoromethyl- 1 ,3-dioxalan-2-yl)-4-thiophensulfonamide 5% water 95% The salt is added directly to the water with stirring to produce the solution, which may then be packaged for use. EXAMPLE 24 : Low Strength Granule 3-(2-Fluoromethyl- 1 ,3-dioxalan-2-yl)-N-[(4-methoxy-6-methyltriazin-2- yl)aminocarbonyl]-4-thiophenesulfonamide 0.1 % attapulgite granules (U.S.S. No. 20-40 mesh) 99.9% The active ingredient is dissolved in a solvent and the solution is sprayed upon dedusted granules in a double-cone blender. After spraying of the solution has been completed, the material is warmed to evaporate the solvent. The material is allowed to cool and packaged. EXAMPLE 25 : Wettable Powder 3-(2-Fluoromethyl- 1 ,3-dioxalan-2-yl)-N-[(4-methoxy-6-methyltriazin-2- yl)aminocarbonyl]-4-thiophenesulfonamide 40% dioctyl sodium sulfosuccinate 1.5% sodium ligninsulfonate 3% low viscosity methyl cellulose 1.5% attapulgite 54% The ingredient are throughly blended, passed through an air mill, to produce an average particle size under 15 microns, reblended, and sifted through a U.S.S. No. 50 sieve(0.3mm opening) before packaging. All compounds of the invension may be formulated in the same manner. EXAMPLE 26 : Granule wettable powder of Example 25 15% gypsum 69% potassium suifate 16% The ingredients are blended in rotating mixer and water sprayed on to accomplish granulation. When most of the material has reached the desired range of 1.0 to 0.42 cm (U.S.S. #18 to 40 sieves), the granules are removed, dried, and screened. Oversized material is crushed additional material in the desired range. These granules contain % active ingredient. EXAMPLE 27 : High Strength Concentrate 3-(2-Fluoromethyl- 1 ,3-dioxalan-2-yl)-N-[(4-methoxy-6-methyltriazin-2- yl)aminocarbonyl]-4-thiophenesulfonamide 99% silica aerogel 0.5% synthetic amorphous silica 0.5% The ingredient are blended and ground in a hammer-mill to produce a material essentially all passing a U.S.S. No. 50 screen (0.3 mm opening). The concentrate may be formulated further if necessary. EXAMPLE 28 : Wettable Powder 3-(2-Fluoromethyl-l,3-dioxalan-2-yl)-N-[(4-methoxy-6-methyltriazin-2- yl)aminocarbonyl]-4-thiophenesulfonamide 90% dioctyl sodium sulfosuccinate 0.1% synthetic fine silica 9.9% The ingredient are blended and ground in a hammer- mill to produce particles essentially all below 100 microns. The material is sifted through a U.S.S. No. 50 screen and the packaged. EXAMPLE 29 : Wettable Powder 3-(2-Huoromethyl- 1 ,3-dioxalan-2-yl)-N-[(4-methoxy-6-methyltriazin-2- yl)aminocarbonyl]-4-thiophenesulfonamide 40% sodium ligninsulfonate 20% montmorillonite clay 40% The ingredients are throughly blended, coarsely hammer-milled and then air- milled to produce particles essentially all below 10 microns in size. The material is reblended and the packaged. EXAMPLE 30 : Oil Suspension 3-(2-Fluoromethyl- 1 ,3-dioxalan-2-yl)-N-[(4-methoxy-6-methyltriazin-2- yl)aminocarbonyl]-4-thiophenesulfonamide 35% blended of polyalcohol carboxylic ester and oil soluble petroleum sulfonate 6% xylene 59% The ingredients are combined and ground together in a sand mill to produce particle essentially all below 5 microns. The product can be used directly, extended with oil, or emulsified in water. EXAMPLE 31 : Dust 3-(2-Huoromethyl-l,3-dioxalan-2-yl)-N-[(4-methoxy-6-methyltriazin-2- yl)aminocarbonyl]-4-thiophenesulfonamide 10% attapulgite 10% pyrophyllite 80% The active ingredient is blended with attapulgite and then passed through a hammer-mill to produce particles substantially all below 200 microns. The ground concentrate is then blended with powdered pyrophyllite until homogeneous. EXAMPLE 32 : Emulsifiable Concentrate 3-(2-Huoromethyl- 1 ,3-dioxalan-2-yI)-N-[(4-methoxy-6-methyltriazin-2- yl)aminocarbonyl]-4-thiophenesulfonamide 10% chlorobenzene 84% sorbitan monostearate and polyoxyethylene condensates thereof 6% The ingredients are combined and stirred to produce a solution which can be emulsified in water for application. EXAMPLE 33 Pie-emergence test To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with 5 parts by weight of acetone, 1 part by weight of alkylaryl polyglycol ether of emulsifier is added and the concentrate is diluted with water to the desired concentration Seeds of the test plants are shown in normal soil and, after 24 hours, watered with the preparation of the active compound. It is expedient to keep constant the amount of water per unit area. The concentration of the active compound in the preparation is of no importance, only the amount of active compound applied per unit area being desicive. 127 After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control. The figures denote : 5 0% = no action (like untreated control) 20% = slight effect 70% = herbicidal effect 100% = total destruction. In this test, the active compounds(I) according to the preparation Examples i o exhibit a better herbicidal activity against nomo- and dicotyledon weeds. EXAMPLE 34 Post-emergence test To produce a suitable preparation of active compound, 1 part by weight of 15 active compound is mixed with 5 parts by weight of acetone, 1 part by weight of alkylaryl polyglycol ether of emulsifier is added and the concentrate is diluted with water to the desired concentration. Test plants which have a height of 5 - 15 cm are sprayed with the preparation of the active compound in such a way as to apply the particular amounts 0 of active compound desired per unit area. The concentration of the spray liquor is so chosen that the particular amounts of active compound desired are applied in 2,000 I of water/ha. After three weeks, the degree of damage to the plants is rated in % damage in comparasion to the development of the untreated control. The figures denote : 5 0% = no action (like untreated control) 20% = slight effect 70% = herbicidal effect 100% = total destruction. In this test, the active compounds© according to the preparation Examples exhibit a better herbicidal activity against mono- and dicotyledon weeds. It is understood that the specification and examples are illustrative but not 5 limitative of the present invention and that other embodiments within the spirit and scope of the invention will suggest themselves to those skilled in the art The herbicidal proficiency of the active ingredients of the present invention is evident from the test results which are recorded in following Tables. The following Tables are represented pre- and post-emergence herbicidal i o evaluation of following "test compounds ". 5 C PLANT RESPONSE SCREENING (Herbicide) Comp. TYPE kg/ha SORBI ECHOR BROJA DIGSA PANDI SOLNI AESIN ABUTH XANSI CAGHE No. (SETVI) [AGRSM] 1 PRE .05 90 90 90 70 90 20 40 65 80 100 POST .05 70 90 100 20 0 0 60 25 70 100 2 PRE .05 100 100 100 90 100 20 40 50 90 100 POST .05 90 100 100 40 10 90 100 60 60 3 PRE .05 65 30 40 15 10 20 0 50 25 POST .05 10 20 30 20 0 0 0 0 0 0 PLANT RESPONSE SCREENING (Herbicide) Comp. TYPE kg/ha SORBI ECHOR BROJA DIGSA PANDI SOLNI AESIN ABUTH XANSI CAGHE No. (SBTVI) [AGRSM] PLANT RESPONSE SCREENING (Herbicide) Comp. TYPE kg/ha SORBI ECHOR BROJA DIGSA PANDI SOLNI AESIN ABUTH XANSI CAGHE No. (SETVI) [AGRS ] S2 PRE .06 SO 90 60 70 85 25 60 70 70 60 POST .05 90 100 90 60 70 50 90 60 70 53 PRE .06 20 30 0 20 20 0 0 0 0 60 POST .05 60 25 20 20 40 20 30 0 0 55 PRE .06 90 80 60 80 90 20 80 80 90 100 POST .05 100 90 80 70 65 40 100 90 90 56 PRE .05 90 30 POST .05 7) 60 90 S PRE .05 80 25 30 35 5 O 35 20 75 90 POST .05 100 80 30 50 90 25 100 60 70 65 1 PRE .1 £ 20 73 0 70 0 0 0 80 POST .1 0 55 80 0 0 20 0 0 0 80 PLANT RESPONSE SCREENING (Herbicide) Comp. TYPE kg/ha SORBI ECHOR BROJA DIGSA PANDI SOLNI AESIN ABUTH XANSI CAGI No. (SETVI) [AGRSMJ PLANT RESPONSE SCREENING (Herbicide) Comp. TYPE kgΛia SORBI ECHOR BROJA DIGSA PANDI SOLNI AESIN ABUTH XANSI CAGHE No. (SETVI) * [AGRSM] PLANT RESPONSE SCREENING (Herbicide) Comp. No. TYPE kg/ha UPLAND WEED SPECIES PADDY WEED SPECIES LYPES TRZAW GLXMX ZEAMX DACGL AMAVI SETV1 RUMJA POLHY AESIN CAGHE ORYSA ECHOR CYPDI ANEKE (SETVI) (COMCO) PLANT RESPONSE SCREENING (Herbicide) Comp.No. TYPE kg/ha UPLAND WEED SPECIES PADDY WEED SPECIES LYPES TRZAW GLXMX ZEAMX DACGL AMAVI SETVI RUMJA POLHY AESIN CAGHE ORYSA ECHOR CYPDI ANEKE (SETVI) (COMCO) 18 PRE .1 95 10 100 90 65 90 (90) 95 100 65 60 80 40 0 POST .1 70 10 90 65 35 100 (40) 70 80 100 100 20 65 100 10 19 PRE .1 90 90 100 100 80 90 (100) 70 100 90 95 100 100 100 70 POST .1 70 40 100 90 100 100 (80) 80 100 90 100 100 100 95 0 23 PRE .1 100 10 100 100 80 90 (100) 75 100 100 90 100 100 90 90 POST .1 30 0 100 100 100 100 (70) 100 100 100 100 70 100 65 30 • 24 PRE .1 100 0 100 100 80 90 (100) 75 100 100 100 100 95 100 70 POST .1 85 0 100 100 70 100 (60) 90 100 100 100 80 90 100 30 31 PRE .1 90 90 70 100 80 90 (100) 80 100 70 90 100 90 100 60 POST .1 70 80 90 100 100 100 (100) 100 100 90 100 70 100 100 40 32 PRE .1 70 25 20 100 70 100 (100) 60 100 25 40 60 60 100 0 POST .1 70 35 70 90 75 80 (70) 60 90 65 30 65 70 100 0 33 PRE .1 30 20 30 90 70 90 (100) 70 90 25 90 100 100 100 60 POST .1 100 60 100 100 100 100 (100) 100 100 100 100 90 100 100 0 PLANT RESPONSE SCREENING (Herbicide) Comp.No. TYPE kg/ha UPLAND WEED SPECIES PADDY WEED SPECIES LYPES TRZAW GLXMX ZEAMX DACGL AMAVI SETVI RUMJA POLHY AESIN CAGHE ORYSA ECHOR CYPDI ANEKE (SETVI) (COMCO) 34 PRE .1 70 40 10 20 70 100 (100) 30 90 10 60 100 100 100 60 POST .1 100 40 70 90 100 100 (100) 100 90 90 30 100 100 100 30 35 PRE .1 70 10 20 10 20 90 (90) 40 80 0 10 90 70 100 0 POST .1 100 10 60 60 80 70 (60) 40 60 10 20 85 80 100 0 36 PRE .1 30 0 10 0 0 0 (0) 0 60 0 0 60 0 100 15 POST .1 65 0 55 0 15 50 (55) 60 50 30 0 60 0 100 0 37 PRE .1 100 10 100 100 70 90 (100) 70 100 100 100 80 90 70 90 POST .1 100 25 100 100 100 100 (100) 90 100 100 100 90 100 100 30 38 PRE .1 100 10 100 65 60 90 (100) 70 90 90 60 90 25 100 60 POST .1 100 10 100 100 100 100 (100) 100 100 100 100 30 70 100 0 39 PRE .1 100 20 90 90 10 90 (100) 70 90 70 60 90 60 0 0 POST .1 100 20 100 100 70 100 (100) 90 100 100 100 35 80 100 0 67 PRE .1 30 0 0 0 60 70 (65) 0 20 0 40 80 60 70 0 POST .1 40 35 30 0 70 100 (40) 20 10 80 70 65 80 0 PLANT RESPONSE SCREENING (Herbicide) Comp. No. TYPE kg/ha UPLAND WEED SPECIES PADDY WEED SPECIES LYPES TRZAW GLXMX ZEAMX DACGL AMAVI SETVI RUMJA POLHY AESIN CAGHE ORYSA ECHOR CYPDI ANEK (SETVI) (COMCO) PRIMARY SCREENING (Herbicide) Comp. No. TYPE kg/ha ZEAMX GLXMX GOSHI TRZAW ORYSA SORBI ECHOR BROJA DIGSA PANDI SOLNI AESIN ABUTH XANSI CAGH (SETVI) [AGRSM) PRIMARY SCREENING (Herbicide) PRIMARY SCREENING (Herbicide) Comp. No. TYPE kg/ha ZEAMX GLXMX GOSHI TRZAW ORYSA SORBI ECHOR BROJA DIGSA PANDI SOLNI AESIN ABUTH XANSI CAGH (SETVI) [AGRSM] PRIMARY SCREENING (Herbicide) Comp. No. TYPE kg/ha ZEAMX GLXMX GOSHI TRZAW ORYSA SORBI ECHOR BROJA DIGSA PANDI SOLNI AESIN ABUTH XANSI CAGHE (SETVI) [AGRSM) PRIMARY SCREENING (Herbicide) Comp. No. TYPE kgflia ZEAMX GLXMX GOSHI TRZAW ORYSA SORBI ECHOR BROJA DIGSA PANDI SOLNI AESIN ABUTH XANSI CAGHE (SETVI) [AGRSM} PRIMARY SCREENING (Herbicide) Comp. No. TYPE kg/ha ZEAMX GLXMX GOSHI TRZAW ORYSA SORBI ECHOR BROJA DIGSA PANDI SOLNI AESIN ABUTH XANSI CAGHE (SETVI) [AGRSM) 64 PRE .1 10 40 50 0 65 60 40 60 30 80 40 65 40 90 90 .05 0 20 0 0 60 60 30 30 40 20 30 20 20 65 90 .025 0 0 0 0 30 30 10 0 0 0 20 0 0 0 80 .012 0 0 0 0 0 0 0 0 0 0 20 0 0 0 60 .006 0 0 0 0 0 0 0 0 0 0 10 0 0 0 40 POST .1 10 80 10 0 30 70 60 70 30 100 40 100 30 80 90 .05 0 80 10 0 40 70 40 65 30 100 40 90 20 100 100 .025 0 70 0 0 30 60 10 40 10 100 30 40 0 100 .012 0 70 0 0 20 40 0 30 0 100 20 10 0 30 40 .006 0 65 0 0 10 30 0 10 0 80 10 0 0 20 PRIMARY SCREENING (Herbicide) PRIMARY SCREENING (Herbicide) PRIMARY SCREENING (Herbicide) PRIMARY SCREENING (PADDY SUBMERGED)- Herbicide PRIMARY SCREENING (PADDY SUBMERGED)- Herbicide PRIMARY SCREENING (PADDY SUBMERGED)- Herbicide PRIMARY SCREENING (PADDY SUBMERGED)- HeΛicide 39 .05 20 30 30 70 70 40 63 .05 40 20 40 61 .1 60 30 20 30 0 40 40 PRIMARY SCREENING (PADDY SUBMERGED)- Herbicide 79 .05 40 50 10 30 40 30 80 .05 70 20 10 30 40 PRIMARY SCREENING (PADDY SUBMERGED)- Herbicide 10 60 60 100 60 60 50 11 40 40 70 60 60 12 2 .1 50 60 20 80 100 70 13 2 .125 40 50 30 30 70 30 14 2 .1 10 0 30 60 60 40 15 2 .1 30 0 20 60 40 30 16 2 .125 60 30 80 80 30 70 17 2 .125 0 30 50 40 60 18 2 .1 10 20 0 70 50 70 19 2 .1 90 90 90 90 100 100 23 2 .1 60 90 100 100 100 100 24 2 .1 50 100 100 100 100 100 PRIMARY SCREENING (PADDY SUBMERGED)- Herbicide

Claims: WHAT IS CLAIMED IS 1. A compound of thiophenesulfonylurea derivatives having the following general formula (I) O W II II P— S — NH — C — N — A ( I ) II I O R 3 wherein, P is P-l, P-2 or P-3 as followings ( PI ) ( P2 ) ( P3 ) wherein, R 1 is H, C r C 3 alkyl, C,-^ haloalkyl, halogen, CN, N0 2 , C C 3 alkoxy, C,- C 3 haloalkoxy, SO j NR-R 11 , C,-^ alkylthio, C,-C 3 alkylsulfinyl, C,- C 3 alkylsulfonyl, SCHF 2 , NH 2 , NHCH 3 , N(Me) 2 , C j - alkyl substituted with C j - alkoxy, C j - haloalkoxy, SH, SCH 3 , CN or OH ; or C0 2 R πι ; and then R 1 is H, C,-C 4 alkyl, C 2 -C 3 cyanoalkyl, methoxy or ethoxy ; R π is H, C j- alkyl, C 3 -C 4 alkenyl, or when taken together connecting R 1 and R π , -(CH^-, -(CH 2 ) 4 -, -(CH 2 ) 5 - or CH 2 CH 2 OCH 2 CH 2 -, may be formed ; R m is C r C 4 alkyl, C 3 - alkenyl, C 3 -C 4 alkynyl, C C 4 alkyl substituted with 1 ~ 3 halogens or cyano groups, C 5 -C 6 cycloalkyl, Q- cycloalkylalkyl or C 2 -C 4 alkoxyalkyl ; Ris wherein, a is O or S ; R 2 is - alkyl substituted with 1 ~ 3 halogens ; R 4 and R 5 are respectively C j -C 4 of alkyl; and R 6 and R 7 are respectively H, C r C 3 alkyl or -Q haloalkyl ; E is CH 2 orsinglbond ; R 3 is H or CH 3 ; Wis O or S ; A is Al, A2, A3, A4, A5, A6 or A7 asfollowings ; A4 Al A2 A3 A5 A6 A7 wherein, Xis H, C,-C 4 alkyl, C r C 4 alkoxy, C r C 4 haloalkoxy, C C 4 haloalkyl, C r C 4 haloalkylthio, -C 4 alkylthio, halogen, C 2 -G -alkoxyalkyl, C 2 - alkoxyalkoxy, amino, C j - alkylamino, dKC j - alkyl) amino or C 3 -C 5 cycloalkyl ; Y is H, C j - , alkyl, C r C 4 alkoxy, C r C 4 haloalkoxy, C,-C 4 haloakylthio, C r C 4 alkylthio, C j - alkoxyalkyl, C 2 -C 5 alkoxyalkoxy, amino, C j - alkylamino, di(C 1 -C 3 alkyl)amino, C 3 -C 4 alkenyloxy, C 3 -C 4 alkynyloxy, C 2 -C 5 alkylthioalkyl, C ] -C 4 haloalkyl, C 2 -C 4 alkynyl, azido, cyano, C^ alkylsulfinylalkyl, C^ alkylsulfonylalkyl, CH j OH, G,-C 5 cycloalkyl, O II C j - cycloalkoxy, C 2 -C. alkylthioalkoxy, -C-R 8 , CH 3 I or -N-OCH 3 ; m is 2 or 3 ; L 1 and L 2 are independently O or S ; R 4 and R 5 are independently C,- alkyl ; R 8 is H or CH 3 ; Z is CH, N, CCH 3 or CC j H j ; Y 1 is O or CH 2 ; X 1 is CH 3 , OCH 3 , OC^H j or OCHF 2 ; Y 2 is CH 3 , CH j CH j , OCH 3 , OCH j CH,, SCH 3 or SCH 2 CH 3 ; X 2 is CH 3 , CH j CHa, or CH j CE, ; Y 3 is H or CH 3 ; X 3 is CH 3 or OCH 3 ; Y 4 is CH 3 , OCH 3 , QsZ xx,, CH 2 OCH 3 or Cl ; X 4 is CH 3 , OCH 3 , O H,, CH 2 OCH 3 or Cl ; and these may be an agriculturally suitable salt, and then, (1) if X is Cl, Br, F or I, Z is CH and Y is OCH 3 , OC-ft, NCH 3 (OCH 3 ), NH 2 , NHCH 3 , N(CH 3 ) 2 or OCHF 2 ; (2) if X or Y is OCHF 2 , Z is CH ; (3) X 4 and Y 4 are not Cl simultaneously ; (4) if W is S, R 3 is H, A is A„ Z is CH or N and , Y is CH 3 , OCH 3 , OCH j C^, CH 2 θCH 3 , C^, CF 3 , SCH 3 , OCH j CH:^^, OCH j C≡CH, OCH j CB CH,, CH(OCH 3 ) 2 or (5) if a number of total carbon atoms of X and Y is more than 4, a number of carbon atoms of R 2 is 4 or less than 4. 2. A compound as defined in claim 1, wherein W is O ; E is single bond ; and R 3 is H. 3. A compound as defined in claim 1, wherein R l is selected from the group consisting of H, halogen, C j - alkyl, C j -C^ alkoxy, C j - haloalkyl, C j - alkylthio, haloalkoxy and CH 2 CN ; X is selected from the group consisting of C,-C 2 alkyl, C j - alkoxy, Cl, F, Br, I, OCHF 2 , CILJF, CF 3 , OO^OLP, OCH 2 CHF 2 , OCH 2 CF 3 , CH 2 C1 and CH 2 Br ; and Y is H, -C j alkyl, C r alkoxy, CH CH,, CH j OCH j CH,, NHCH 3 , N(OCH 3 )CH 3 , N(CH 3 ) 2 , CF 3 , SCH 3 , OCH 2 CH=CH 2 , OCH 2 C≡CH, OCH j C^OCH,, C^SCH,, OCHF 2 , OCF 2 Br, SCHF 2 , cyclopropyl, C ≡ CH or C≡C-CH 3 , and then R 4 and R 5 are - alkyl, R 8 is H or CH 3 , L* and L 2 are O or S, and m is 2 or 3 . 4. A compound as defined in claim 1, wherein A is A j ; X is CH 3 , C^, OCH 3 , OCH 2 CH 3 , Cl or OCHF 2 ; and Y is CH 3 , OCH 3 , OCft, Hj, CH 2 OCH 3 , NHCH 3 , OKOCH,), or cyclopropyl. 5. A compound as defined in claim 1, wherein R 2 is CH^, CΑ 2 CH^F, CHFCH 3 , CH 2 C1, CH 2 Br, CHC1 2 , CHFCl, CH j CH^Cl, CHC1CH 3 , CHF 2 , CHC1CH 2 C1, CHFCH 2 C1, CHFCH j F or CE^CHF j . 6. A compound as defined in claim 1, wherein said general formula® is 3-(2- fluoromethyl-l,3-dioxalan-2-yl)-N-[(4-methoxy-6-methyltriazin-2- yl)aminocarbonyl]4-thiophenesulfonamide. 7. A compound as defined in claim 1, wherein said general formula® is N- [(4,6-dimethoxytriazin-2-yl)aminocarbonyl]-3-(2-fluoromethyl-l,3- dioxalan-2-yl)-4-thiophenesulfonamide. 8. A compound as defined in claim 1, wherein said general formula® is 3-(2- fluoromethyl- 1 ,3-dioxalan-2-y 1 )-N-[(4-methoxy-6-methylpyrimidin-2- yl)aminocarbonyl]4-thiophenesulfonamide. 9. A compound as defined in claim 1, wherein said general formula® is 2-(2- fluoromethyl -1 ,3-dioxalan-2-yl)-N-[(4-methoxy-6-methyltriazin-2- yl)aminocarbonyl]-3-thiophenesulfonamide. 10. A compound as defined in claim 1, wherein said general formula® is N- [ (4,6-dimethoxytri azin-2-yl )am inocarbonyl]-2-(2-fl uoromethyl- 1 ,3-oxalan- 2-yl)-3-thiophenesulfonamide. 11. A compound as defined in claim 1, wherein said general formula® is 4- (1 , 1 -diethoxy-2-fiuoroethyI)-N-[(4-methoxy-6-methylprimidin-2- yl)aminocarbonyl]-3-thiophenesulfonamide. 12. An intermediate compound of the formula® in the claim 1 having the following general formula(IV) O II P— S — NH 2 ( IV ) II o wherein, P is as defined in the above claim 1. 13. A compound as defined in claim 12, wherein said formula(IV) is 3-(2- fluoroethyl-l,3-dioxalan-2-yl)-4-thiophenesulfonamide or 2-(2- fluoromethyl- 1 ,3-dioxaIan-2-yl)-3-thiophenesulfonamide. 14. Herbicides containing at least one of the following general formula® of thiophenesulfonylurea derivatives as an active ingredient O W || || P— S — NH — C — N — A ( I ) II I O R 3 wherein , P, W, R and A are respectively as defined in said claim 1. 15. A method for controlling weeds by which applies effective amount of at least one of the following general formula(I) of thiophenesulfonylurea derivatives in weedy area 5 o w II II P— S — NH — C — N — A ( I ) II I ι o O R 3 wherein , P, W, R and A are respectively as defined in said claim 1. 15 20 25 Jϋ

Inventors: JEON DONG JU, KIM DAE WHANG, KIM TAE JUN, PARK SANG SOON, WOO JAE CHUN, JEON, DONG, JU, KIM, DAE, WHANG, KIM, TAE, JUN, PARK, SANG, SOON, WOO, JAE, CHUN
Applicants: KOREA RES INST CHEM TECH, KOREA RESEARCH INSTITUTE OF CHEMICAL TECHNOLOGY
Application year: 1992
Main classification: A01N43
IPC codes: A01N47, C07D409, C07D491, C07D521