HERBICIDAL SULFONYL UREA DERIVATIVES

BACKGROUND OF THE INVENTION

Field of the Invention

The present invention relates to novel sulfonyl urea derivatives of the following formula (I) having erythio-type stereoisomer as herbicides for treatment of pie-emergence and/or post-emergence, their use and composition as agriculturally suitable herbicides.

wherein,

P and Q, as equivalent or different group respectively, are CH or N, and present as aromatic ring including P and Q a.s benzene or pyridine ring ; O ()

R is H, R ^a - C - or R' ^~ X ^J - C - group, wherein R is C, ~C ₄ alkyl, C, ~C, haloalkyl, C _^ ~C alkenyl or C, ~C ₄ alkynyl group, wherein X ^'Δ is O, S,

NH or NR ^J group; R' is H or CH, group; and X and Y are independently halogen atom, C ,~C alkyl, C _t ~C alkoxy or C,~C, haloalkoxy group.

Description of the Prior Art

It is publicly well-known that sulfonyl urea derivatives possess a herbicidal activity. Such examples containing sulfonyl urea are;

(1) Korea Patent publication No. 93-9825 discloses the compound having the following fonnula(A)

Oil

wherein, R is haloalkyl ;

X and Y are independently CH,, OCH, or Cl etc. ; Z is CH or N.

(2) Korea Patent publication No. 93-9507 discloses the compound having the following formula(B)

Oi l

wherein,

R, X, Y and Z are as previously defined, P and Q are differently N or CH.

If R group of the above formula(A) and (B) includes asymmetric carbon atom, then the above compound has two stereoisomers which are threo- and erythro-type by reason of two asymmetric carbon atom. But herbicidal activity and selectivity of the above stereoisomers have been not disclosed.

SUMMARY OF THE INVENTION The object of the present invention is to provide novel sulfonyl urea derivatives having very prominent herbicidal activities toward rice and wheat and also possess a good selectivity for annual and perennial weed, especially a barnyard grass.

Another object of this invention is to provide herbicidal eompositons containing said derivatives as active compounds.

BRIEF DESCRIPTION OF THE INVENTION 5 Fig. 1 is stereoconfiguration based upon X-ray crystallography analysis of the compound manufactured by EXAMPLE 1. Fig. 2 is stereoconfiguration based upon X-ray crystallography analysis of the compound manufactured by EXAMPLE 9.

o DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to herbicidal sulfonyl urea derivatives with substituent of erythro-type stereoisomer having the following formula(I), which have herbicidal selectivity toward rice and wheat, and their agriculturally suitable salts.

wherein,

P, Q, R, R', X and Y are a.s previously defined.

A preferred group of erythro-type stereoisomer of the ahove formula(I), in view of 0 a strong activity and a good selectivity is a.s follows :

(1) Benzene(P and Q are independently CH)

(2) Pyridine(P is N, and Q is CH)

(3) R is hydrogen atom

(4) R' is hydrogen atom 5 (5) R is acetyl group

(6) X and Y are methoxy group.

These compounds can easily control barnyard grass a.s well as a perennial weed causing UOuble for rice and can be used agriculturally as herbicidal composition for rice.

Especially the following compounds have a good selectivity for rice :

Erythro N-[(4,6-dimethoxy-pyrimidin-2-yl)aminocarbonyl]-2-(2-nuoro-l -hydro- xy-n-propyl)-3-pyridinesulfonamide,

Erythro N-[(4,6-dimethoxy-pyrimidin-2-yl)aminocarbonyl]-2-(2-lluoro- l-hydiO- xy-/7-propyl)-benzenesulfonamide, etc..

The erythro-type compounds of the above formula(I) according to the present invention have more prominent herbicidal activity than threo-type or mixture of erythro- and threo-type. Furthermore, the erythro-type compounds of the above foιτnula(I) may be used as herbicides or active ingredient of herbicidal composition because of a good selectivity for rice and wheat.

A pure compound of erythro-type having the above formula(I) according to the present invention can be prepared by reactions described in herein below, but should not be constructed to be limited hereto.

The compound of the above formula(I), in which R is hydrogen atom, can be obtained by hydrolyzing the compound of the above foιτnula(I), where R is acyl group such as acetyl group, in present of alkali.

In order to hydrolyze the above acyl group, alkali such as LiOH, KOH, NaOH, Li,CO,, Na O,, K ₂ CO,, etc., preferably LiOH, may be used.

The above hydrolysis reaction is carried out under water or organic solvent, as a mixture of water with unreacting solvent such as methanol, ethanol, acetone, tetrahydrofuran, dimethylformamide, etc., or solvent alone. The hydrolysis occurs at the temperature of 0 - 80 C in a reaction time of 1-24 hours, and then the obtained product may be easily seperated by acidifying with aqueous HCl solution.

As an other process, after acidifying, the obtained product is extracted with methylene chloride, ethyl acetate, etc. and then concentrated to obtain the final product.

If necessary, a pure product can be obtained by purification using HPLC.

The hydrolysis in the above reaction is carried out a.s shown in the following reaction scheme.

Alkali

hydrolysis

( I )

( I )

wherein,

P, Q, R', X and Y are respectively defined a.s the above foπnula (I), and R is defined as the above formula (I) except of hydrogen atom.

Also, the compounds of the above formula (I) according to the present invention can be prepared by reacting the erythro-type compound having the following formula (II) with the compound having the follwoing formula (III).

( π ) ( HI )

( I )

wherein,

P, Q, R, R', X and Y are respectively defined as the above formula(I).

In the above reaction, unreacting solvent such a.s tetrahydrofuran, acetone, acetonitrile, dio xane, methylene chloride, toluene, buianone, pyridine, dimethylfoιτnamide, etc., may be used.

The reaction may he preferably carried out under strong base such as DBU or DABCO, etc. in a small quantity at the temperature of 20-80 "C . The above reaction is referred to in U.S. patent No. 4,443,245 and thereafter the desired product can be obtained by acidifying by the method mentioned in European Patent No. 44,807. If necessery, a pure product can be obtained by purification by HPLC. Said, DBU represents 1,8 - diazabicyclo[ 5.4.0] undec-7-ene, and DABCO represents 1,4-diazabicyclo [2.2.2]octane.

Also, the compound of the formula(III) used for preparing the above formula(I) can be easily obtained by the prior art.

On the other hand, the erythro-type of the above formula(II) can be prepared by die following reaction scheme.

( IV ) ( II )

wherein,

P, Q and R are respectively defined as the above.

In the above reaction, the primary sulfonamide of erythro-type having the above formula(II) can be prepared by treating N-r-butylsulfonamide of the above formula(IV) with an acid such as trifluoroacetic acid (TFA) at the temperature of 0~50T_. .

Also, the erythro-type of the above formula(IV) used in the above reaction can be

prepared by common acylation of the following formula(V). The pure erythro-type of the above formula(IV) can be seperated from mixture of threo- and erythro-type by purification such as column chromatograph, HPLC or prep-TLC.

The compound of the following l rmula(V) can be prepared by selective reduction of the compound of the following formula(VI) with selective reductant such as diisobutylaluminum hydride.

wherein,

P and Q are respectively defined a.s the above,

DIBAL • H is diisobutylaluminum hydride.

In the above reaction, preferably P is N and Q is CH.

The pure erythro-type of the above formula(V) can be easily purified using column chromatograph.

The compound of the above formula(IV) can also be prepared by another process as shown in the followinsi reaction.

( VIII )

chromatograph

( IV )

wherein,

P and Q are respectively defined as the above formula(I), R is defined as the above formula(I) except of hydrogen atom, L is alkoxy, N(CH,) _: or NCH,(()CH,), etc..

The above reaction process has been disclosed in Korea Patent Application No.

91-3704 and No. 91-3014. ;?-Butyl lithium of 2 equivalents are added in the compound of the above formula(VII) in THF solvent for 1-24 hours at -80 - + 30t to

II obtain dilithio salt, and then L-C-CHF-CH, is added at -70 - -80C to obtain ketone compound. Hydroxy compound is obtained by reduction of the ketone compound with

NaBH ₄ , and then the compound of formula (VII) wherein R is acetyl group is obtained by acylation under acetic anhydride, DMAP and pyridine.

The pure erythro-type of the above formula (IV) can be easily obtained by separat ion and purification techniques such a.s HPLC, column chromatograph, prep-TLC, etc..

On the other hand, salts of the compound of the above formula(I) which are also useful as herbicide, can be prepared by various methods according to prior art. For example, metal salts of the compound can be prepared by reacting the 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 carried out by directly reacting a solution containing cation for exchange with the solution of salt of formula(I), for example aqueous solution of alkali metal or quaternary amine salt. This method is useful when the desirable salt is water soluble, especially sodium, potassium or calcium salt.

The above manufacturing methods are summarized briefly, and the methods can be cairied out easily by a person skilled in the technical field for manufacturing sulfonyl urea or organic composition.

The compounds of the above foιτnula(I) according to the present invention may be specified as the following Table 1.

Table 1.

Isomer Q R R' m.p.CC)

erythro CH CH H H 166 - 168

Isomer P Q R R ' m.p.(C )

O

II erythro CH CH CCHXHXH, H () erythro N CH CCHXHXH, H

() II erythro CH N CCHXHXH, H

()

II erythro CH CH COCH, H 186 - 192

()

II erythro N CH COCH, H

0

II erythro CH N COCH, H () erythro CH CH COCHXH, H 168 - 170

() || erythro N CH COCHXH, H

() erythro CH N COCHXH, H

()

II erythro CH CH COCHXH=CH, H ~_ ~_

Isomer P Q R R ' m.p.(t )

II erythro N CH COCH _: CH=CH ₂ H

O erythro CH N COCHXH=CH ₂ H

()

II erythro CH CH COCHX≡CH H

()

II erythro N CH COCHX≡CH H ()

II erythro CH N COCHX≡CH H

erythro CH CH H CH, 139 - 140 ()

II erythro CH CH CCH, CH, 162- 164

CH,

CH,

CH,

CH,

Isomer P Q R R' m.p.CC)

threo CH CH H H 189-191

O

II threo CH CH CCH, H 194- 196

threo N CH H H 173 - 175

() threo N CH CCH, H 190 - 192

threo CH N H H

() threo N CH CCHXH=CH, H

Isomer R R ^* m.p.CC )

O

II threo CH N CCHXH=CH ₂ H ()

II threo CH CH COCH, H

O

II threo N CH COCH, H

0

II threo CH N COCH, H

0 threo CH CH COCHXH, H

()

II threo N CH COCHXH, H

()

II threo CH N COCHXH, H

()

II threo CH CH COCHXH=CH ₂ H ()

II threo N CH COCHXH=CH _: H ()

II threo CH N COCHXH=OL H

Isomer R R ^* m.p.(C)

() threo CH CH COCHX≡CH H

() threo N CH COCHX≡CH H

O

II threo CH N COCHX≡CH H

threo CH CH

threo CH CH

threo N CH

threo N CH

threo CH N

threo CH N

The sulfonyl urea derivatives having erythro-type stereoisomer of the above formula(I) according to the present invention are useful as herbicides. The applied method is given below.

[Utility]

The compounds according to the present invention represent very high activity as pre- or post- emergence herbicides and water surface U'eatment or leaf U'eatment herbicides for rice.

The used amount of compound of the present invention is decided by several factor, that is, kinds of weeds, climate or weather, formulations selected, the applied method or the size of weed etc.

The active ingredients can be generally used from 1 g to 1 kg per hectare. Smaller quantity may be used in soil containing low organic matter or sandy soil, young plant or when the herbicidal effect is need of short-termed duration. The compounds according to the present invention are especially effective as ingredient for control of weed in rice and wheat field, especially leaf-width weed, gra- minaceae weed and annual or perennial weed. The compounds are particularly effective for control of barnyard grass.

The list of weeds controllable by the compounds of the present invention is given below.

[the list of weeds] dicotyledon weeds genus:

Sinapis, Lepidium, G alium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranlhus, Portulaca, Xanthium. Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solan- um, Rorippa, Rotala, Lindemia, Lamium, Veronica, Arbutilon, Emex, Datura, Viola, Galeopsis, Papaver, Ceniaurea. monocotyledon weeds genus:

Echinochloa, Setaria, Panicum, Digitaria, Phleu , Poa, Festuca, Eleusine,

Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon,

Monochoria, Fimbristylis, Sagittaria, Eleocharis , Scirpus, Paspalum,

Dactyloctenium, Agrostis, Alopecurus, Apera, Heteranthera, Leptochloa. Tlie com pounds of the present invention can be used as alone or in combination with two, three or four additives with other herbicides. The appropriate herbicides for mixed-using with the compounds of the present invention are given bleow. It is paiticularly useful for control of weeds to use the mixture of tlie compounds of tlie present invention and the below herbicides. Common Name acetochlor acifiuorfen

AC 252,214 AC 263,499 acrolein alachlor ametryn amitrole AMS asulam assure atrazine

BAS-514 barban benefin bensulfuron methyl bensulide bentazon benzofluor benzoylprop bifenox bromacil bromoxynil butachlor bulhidazole hutralin butylate cacodylic acid CDAA CDEC

CGA 82725 CH-83 chloramben chlorbromuron chlorimuron ethyl chloroxuron chlorporpham chlorsulfuron

chlortoluron cinmethylin clethodim clomazone cloproxydim clopyralid

CMA cyanazine 5 cycloate cycluron cyperquat cyprazine cyprazole cypromid dalapon dazomet

DCPA desmediphan o desmetryn diallate dicamba dichlorbenil dichloi rop dichlofop dielhatyl di enzoquat dinitramine dinoseb 5 diphenamid dipropetryn diquat di ron

DNOC DOWCO 453 ME

DPX-M6 16 DSMA endothall EPTC 0 ethallluralin ethofumesate express fenac fenoxapropethyl fenuron fenuron TCA flamprop fluazifop fluazifophulyl 5 fluazifop-P lluchloralin fluometuron lluorochloridone

Ωuorodifen fluoroglycofen fluridone fomesafen fosamine glyphosaie

haloxyfop hannoney hexaflurate hexazinone

HW-52 imazamethabenz imazapyr imazaquin imazediapyr ioxynil isopropalin isoproturon isouron isoxaben kai'butilate lactofen lenacil linuron MAA MAMA

MCPA MCPB mecoprop mefluidide metlialpropalin methabenzthiazuron meϋiam methazole methoxuron metolachlor metribuzin metsulluron methyl

MH molinate monolinuron monuron monuron TCA MSMA My-93 napropamide naproanilide naptalam neburon nitralin nitrofen nitrolluorfen norea norfrurazon NTN-801 oryzalin oxadiazon oxyfluorfen paraquat pebulate pendimeihalin perfluidone phenmedipham picloram

PPG- 1013 pretilachlor procyazine profiuralin prometon prometryn pronamide propachlor 5 propanil propazine propham prosulfalin prynachlor pyrazon pyrazolate quizalofop quizalofop etliyl SC-2957 ι o secbumeton sethoxydim siduron si azine

SL-49 sulfometuron methyl

TCA tebulhiuron terbacil terhuchlor 15 terbuthylazine terhutol terbutryn thiameluron methyl thiohencarb triallate triclopyr iridiphane trifluralin trimeiuron 20 2,4-D 2,4-DB vernolate X-52 xylachlor Saturn

KH-218 NSK-850

Pyrazoxyfen Dimension 25 CH-900 Mefenacet

TSH-888 Dymron

Dimepiperate Isoxapyrifos

Phenobenzuron JC-940

Esprocab Methylbencah

Phenopylate Benfuresate S-275 Quinclorac Londax NC-31 1 TH-913 HW-52 DEH-112 SKH-301 Bromobutide BAS517H RE45601 RE36290 RO 173664 HOE075032 ICIA6051 DPX ^a 7881 MW801 CG A 136872 DPXV9360 DPXE9636 SL950 ICIA02957 CGAI42464 MY 15 MON7200 WL95481 DPXY6202 MON 15100 SL160 ICIA0224 LS83556 BAS518H CGA131036 DPXL5300 HOE70542 ICIA0604 ICIA0574 LS 46215

[ Formulation ]

Formulations for the use of the compou nds of foιτnu la( I ) can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly.

Sprayable form ulations can be prepared in suitable media and used at spray volumes of from a few liters to several houndred liters per hectare. H igh strength compositions are primarily used as inteπnediates for further formulation. The

9" ⁾ formulations, broadly, contain about .1 ^ to 98.9% by weight of active ingredient(s) and at least one of ( 1) about 0.1%= to 20% surfactant(s) and (2) about 1%» to 99.8% solid or liquid inert diluent(s) are recommended. More specially, the formulations will contain these ingredients in the following approximate proportions:

Table 2.

Lower or higher levels of active ingredient can, of course, be present depending on tlie intended use and the physical properties of the compound. Higher ratios of surface active agent to active ingredient are sometimes desirable, and are achieved by incorporat ion into the formulation or by tank mixing.

Typical solid diluents are mentioned in the writings of Watkins, et l.(" Handbook of Insecti cide Dust Diluents and Carrier" 2nd Ed., Dor land Books, Caldwell, N.J.,) and odier solid diluents can be used.

The more absorptive diluents are preferred for wettable powders and the denser ones for dusts.

Typical liquid diluents and solvents are mentioned in the writings of Marsden ("Solvents Guide", 2nd Ed., Interscience, New York, 1950).

Solubility under 0.1 %: is preferred for concentrated suspension; concentrated

solution is preferably stable against phase separation at 0C .

The surface active agents and thei r using method is mentioned in the writings of McCutcheon (McCulcheon's Detergents and Emulsifiers Annual, Me Publishing Corp. , Ridgewood, N. J.,) and Sisely et al. (Sisely snd Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., New York, 1964).

All the above formulations may contain a small amount of additives to reduce foaming, caking, corrosion and the growth of microorganisms.

The preparation methods of such compositions are well known. A solution can be made only by blending properties and a fine solid composition by blending and pulverizing.

Suspension agents can be made by wet milling method (U.S. Patent No.

3,060,084) and granules and pellets can be made by spraying the active ingredient on preformed granular cairier, or by Agglomeration method (J.E. Browing, "Agglomeration

" Chemical Engineering, Dec. 4,1967, ppl47 / "Perry's Chemical Engineer's Handbook," 5th Ed., Mcgraw-Hill, New York, 1973, pp 8-571Ϊ).

For further information regarding the art of formulations, see for example: US pa¬ tent No. 3,235,361 / 3,309,192 / 2,89 1 ,855, G. C. Kling man, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pp.81-96 / J. D. Fryer and S. A. Evans, "Weed Control H andbook", 5ιh Ed., Blackwell Scientific Publications Oxford, 1968, pp.101-103.

Tlie compounds of the present invention can be used independently and may be used in combination with any other c mmercial herbicides. To specify some more the manufacturing and using of the compounds of the present invention, the detailed example- s are described below.

EXAMPLE 1

Erythro 2-(l-acetoxy-2-fiuoro-/i-propyl)-N-t-butyl-benzenesulfonamid e.

Erythro N-t-butyl-2-(2-πuoro- l -hydι xy-n-ρropyl)-benzenesulfonamide (3.5 g) was dissolved in 50 ml of methylene chloride and herein acetic anhydride ( 1.25 ml ),

pyridine(l.l ml ) and NN-dimethyl aminopyridine(0.12 g) were added. After stirring for 1 hour, the reacting solution was diluted with methylene chloride and washed with

5% hydrochloric acid solution. The seperated organic layer was dried with magnesium sulfate, filtered and concentrated. And then the obtained residue was chromatographed through silicagel using 1 : 3(v/v) solution of ethyl acetate/hexane to afford 3.7 g of the desired product(white solid). m.p. : 134 - 135 C

¹ H ΝMR(200MHz, CDCl,) : δ l .25(s, 9H), 1.36(dd, 3H, _H.H =6.4Hz, J _H . _F =

25.3Hz),2.17(s, 3H), 4.86-5.22(m, IH), 5.47(brs, I H), 6.68(dd, I H, / _{1 J} =3Hz, /„ _.F =18.6Hz),

7.41 -7.71 (m, 3H), 8.04-8.12(m, IH).

IR(KBr) - (C=O) 1715 cm ^"1

Crystal data of product prepared by the above EXAMPLE 1 is the following.

Crystal data Molecular Formula C ₁₅ H ₂₂ FNO ₄ S

Measured Density(D _ι ) 1.3 MgπX

Molecular Weight(M _r ) 331.4

Used Wave Length^ ) : 0.71069 A

Crystal System monoclinic system No. of diffraction data used in measuring lattic constant : 25

Size of unit cell a = 13.693(6) A b = 14.731 (15) A c = 8.737(5) A β = 106.51(5) A

Volume of unit cell (V) : 1690( 1 ) A

Independent Molecularity(Z) : 4

Calculating Density(Dx) : 1.303 Mg πX

Data Collection Used Diffractometer : CAD-4 diffractometer made in

Netherland Enraf-Nonius company o Maximum angle of Scan : θ = 24° Scanning Method : -> I2θ scans Range of Miller Index h=- 15→ 15 k=()→ 16 1=0→9 Absoiption Correction Method : did not correct. measuring method : 3 of standard data were confirmed 5 every time diffraction data was measured.

Change of standard data on measuring no change

No. of Measured Data : 2549

No. of Independent Data 2549

No. of measured data in significant having threefold of standard deviation 0 : 2337 [F>30(F)]

Refinement

Data used in refining F Refined parameter : non-hydrogen atom : atomic coordinates x,y,z and anisotropic 5 temperature factor (u _n ) hydrogen atom : isotropic temperature factor (u) hydrogen atom coupled nitrogen[H(N)] : atomic coordinates x,y,z and isotropic temperature factor (u) No. of parameter refined by the minimum square method 224 0 Final Reliancity factor(R) : 0.0598

Sequencity of refining process variables by the minimum square method (S)

: 3.5233

Manimum differential-composite electron density(ΔPmax) : 0.481 e A ^'3

Minimum differential-composite elect on density(ΔPmin) : 0.349 e A ^"3 No. of data used in refining : 2337 [F>30(F)]

Atomic scattering factor used in X-ray crystalography is described in the Table 3 and stereoconfiguration of innermolecular atoms are given in Figure 1.

Table 3.

EXAMPLE 2

Threo 2-(l-acetoxy-2-fiuoro-/j-propyl)-N-t-butyl-benzenesulfonamid e

From threo N-t-butyl-2-(2-fiuoiO- l-hydi'oxy-n-propyl)-benzenesulfonamide (6 g) was obtained 6.4 g of the desired product (white solid) using the same method of EXAMPLE 1. m.p. : 126 - 127 "C

Η NMR(20()MHz, CDCl,) : <? 1.23(s, 9H), 1.36(dd, 3H, _1I .„=6.4Hz, /„. _F =23.6Hz),

2.18(s, 3H), 4.73-5.1 1(m, IH), 5.54(brs, IH),

6.49(dd, IH, 7 _II .„=3.8Hz, / _π . _F =21.6Hz), 7.41 -7.69(m, 3H), 8.02-8.1 l(m, IH).

IR(KBr) - (C=O) 1715 cm ^"1

EXAMPLE 3

Erythro 2-(l-acetoxy-2-fluoiO-/}-propyl)-benzenesulfonamide Erythro 2-(l-acetoxy-2-fluoro-/j-propyl)-N-t-butyl-benzenesulfonamid e (3.7 g) was dissolved in trifluoroacetic acid(20 ml) after stirring for 24 hours at room temperature was concentrated under vacuum and residue solution was diluted with methylene chloride and washed with 5 ) NaHCO, solution.

The organic layer was dried with magnesium sulfate, filtered and concentrated. and then the concentrated solution was column chromatograped using eluate of ethyl acetate/hexane to afford 2.3 g of the desired product (while solid). m.p. : 105 - 107 ^* C Η NMR(20()MHz, CDCl,) : S 1.33(dd, 3H, J _{]I II} =6.4Hz, 7„. _F =24.6Hz),

2.18(s, 3H), 4.85-5.23(m, IH), 5.55(brs, 2H), 6.53-6.68(m, IH), 7.46-7.75(m, 3H),

8.06-8.13(m, IH). EXAMPLE 4 Threo 2-(l-acetoxy-2-fiuoro-;]-piOpyl)-benzenesulfonamide

The desired product 3.9 g(white solid) was obtained by the same method of EXAMPLE 3 from threo 2-( l-aceioxy-2-fiuoro-/ι-propyl)-N-t-hutyl-benzenesulfonamide

(6.4 g). m.p. : 126 - 128 X.

Η NMR(200MHz, CDCl,) : δ 1.36(dd, 3H, / _H . _H =6.4Hz, J„. _F =24.2Hz),

2.18(s, 3H), 4.75-5.12(m, IH), 5.57(brs, 2H), 6.38-6.53(m, IH), 7.46-7.66(m, 3H),

8.06-8.13(m, IH).

EXAMPLE 5

Erythro 2-( l-acetoxy-2-fluoro-/j-propyl)-N-[(4,6-dimethoxypyrimidin-2-y l)- aminocarbonyl]-benzenesulfonamide [ Compound No. 4 ] Erythro 2-(l-acetoxy-2-fluoro-/7-propyl)-benzenesulfonamide (2.3 g) was dissolved in 20 ml of acetonitrile and herein 2.3 g of phenyl (4,6-dimethoxy pyrimidin-

2-yl) carbamate was added at room temperature. 1 ml of DBU was slowly added dropwised . The reacting solution was stirred for 30 minutes and diluted with 100 ml of methylen chloride. Washed with 50 ml of 5% hydrochloric acid solution and 50 ml of water, the organic layer was dried with magnesium sulfate, filtered and concentrated.

The obtained residue was treated with ethyl acetate/hexane/ethylether to afford 2.9 g of the desired product (white solid). m.p. : 191 ~ 193 C

Η NMR(2()0MHz, CDCl,) : - 1.33(dd, 3H, / _IM ,=6.4Hz, _H.F =24.6Hz), 2.04(s, 3H), 3.96(s, 6H), 4.86-5.25(m, IH),

5.80(s, IH), 6.70-6.82(m, IH), 7.18-7.7()(m, 4H), 8.30-8.40(m, IH), 13.15(brs, IH).

EXAMPLE 6

Threo 2-(l-acetoxy-2-fluoro-;j-propyl)-Λ [(4,6-dimethoxypyrimidin-2-yl)amino- carbonyl]-benzenesulfonamide [ Compound No. 5]

5.3 g of the desired product was obtained using the same method of EXAMPLE 5 from 3.9 g of threo 2-(l-acetoxy-2-fluoiO-/]-propyl)-benzenesulfonamide.

¹ H NMR(200MHz, CDCl,) : δ 1.33(dd, 3H, 7 _{] I} =6.4Hz, J _{1I F} =24.2Hz), 2.04(s, 3H), 3.96(s, 6H), 4.80-5.14(m, IH),

5.80(s, IH), 6.42-6.62(m, IH), 7.23-7.70(m, 4H),

8.27-8.37(m, IH), 12.95(brs, IH).

EXAMPLE 7

Erythro N-[(4,6-dimeihoxypyrimidin-2-yl)aminocarbonyl]-2-(2-fiuoro- 1 -hydroxy- π- propyl)-benzenesulfonamide [ Compound No. 1]

EryUiro 2-(l-acetoxy-2-fluoro-/?-propyl)-N-[(4,6-dimethoxypyrimidin- 2-yl)amino- carbonyl]-benzenesulfonamide (2.9 g) was dissolved in 60 ml of tetrahydrofuran and herein 0.9 g of lithium hydroxide and 10 ml of water were added. After stirring for 12 hours at room temperature, acidified with hydrochloric acid at 0 "C . The reacting solution was diluted with 100 ml of ethyl acetate and once washed with water. The organic layer was dried with magnesium sulfate, filtered and concentrated. The obtained residue was treated with ethyl ether and hexane to efford 2.3 g of the desired product, (white solid) m.p. : 166 - 168 "C 'H NMR(200MHz, CDCl,) : δ 1.33(dd, 3H, J _. „=6.4Hz, /„ _.F =24.6Hz),

3.08(brs, IH), 3.96(s, 6H), 4.86-5.25(m, IH),

5.80(s, IH), 5.89-6.07(m, IH), 7.36-8.24(m, 5H),

12.82(brs, IH).

IR(KBr) - (C=O) 1705 cm ^"1 EXAMPLE 8

Threo N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbony)]-2-(2-iluoro-l -hydroxy-n- propyl]-benzenesulfonamide [ Compound No. 2]

3.0g of the desired product (white solid) was obtained using the same method of

EXAMPLE 7 from threo 2-(l-acetoxy-2-fiuoro-jj-propyl)-N-[(4,6-dimethoxypyrimidin- 2-yl)aminocarbonyl]-benzenesulfonamide(3.7 g). m.p. : 189 - 191 C

¹ H NMR(200MHz, CDCl,) : 1.36(dd, 3H, J,, _u =6.4Hz, „. _F =24.2Hz),

3.0(brs, IH), 3.96(s, 6H), 4.78-5.1 l(m, IH),

5.8()(s, IH), 5.79-5.91(m, IH), 7.22-7.78(m, 4H),

8.1 -8.22(m, IH), 12.75(brs, IH).

IR(KBr) v (C=O) 1691 cm ^"1

EXAMPLE 9

Erythro 2-(l-acetoxy-2-fluoro-.n-propyl)-3-pyridinesulfonamide. 5.0 g of erythro 2-( l-aceioxy-2-fiuoro-n-propyl)-N-( l , l -dimethylethyl)-3- pyridinesulfonamide was dissolved in 20 ml of trifluoroacetic acid. After stirring for 12 hours at 35 t , the reaction solution was concentrated under vacuum. The residue was dissolved in methylene chloride and washed with NaHCO, solution. The organic layer was dried wiUi anhydrous magnesium sulfate and the residue was crystallized with ethyl acetate and hexane to afford 3.0 g of the desired product. m.p. : 141 - 143 ^* C

¹ H NMR(200MHz, CDCl,) : δ 1.55(dd, 3H, 7 _{lι π} =6.5Hz, /„. _r =25Hz),

2.18(s, 3H), 4. 3-5.29(m, IH), 5.68(brs, 2H),

6.55-6.62(m, IH), 7.43-7.50(m, IH), 8.35-8.38(m, IH), 8.82-8.85(m, IH)

Crystal data of the product prepared by the above EXAMPLE 9 is the following.

Crystal Data

Molecular Foπnula

Crystal System Trichlinic system Space Group PI

Molecularity of inner unit lattice(Z) 2 a = 8.529, b =10.270, c = 8.528, * =\ 10.09, β = 99.28,y =1 10.08

No. of independent diffraction data : 1953

Final Reliancity factor 6.199c X-ray Wave Length 1 ,5405

Atomic scattering factor used to X-ray crystalography is described in the following

Table 4 and stereoconfiguration of innermolecular atoms are given in Figure 2.

Table 4.

EXAMPLE 10

Threo 2-(l-acetoxy-2-fluoro-π-propyl)-3-ρyridinesulfonamide

1.6 g of the desired product was obtained using the same method of EXAMPLE 9 from threo 2-(l-acetoxy-2-fiuoro-n-propyl)-N-(l ,l-dimethylethyl)-3-pyridinesulfon- amide (3.0 g) m.p. : 164 - 165 XZ

'H NMR(200MHz, CDCl,) : δ 1.17(dd, 3H, J _IMI =6.5Hz, „. _F =23.9Hz),

2.16(s, 3H), 5.03-5.38(m, IH), 5.79(brs, 2H),

6.54-6.64(m, IH), 7.43-7.49(m, IH), 8.35-8.40(m, IH), 8.80-8.83(m, IH)

EXAMPLE 1 1

Erythro 2-(l-acetoxy-2-fiuoro- 3-propyl)-N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl]-3-pyridinesulfonamide [ Compound No. 10]

5.1 g of the desired product (white solid) was obtained using the same method of EXAMPLE 5 from 3.9 g of erythro 2-( l-acetoxy-2-fluoro-/7-ρropyl-3-pyridinesulfon- amide. m.p. : 218 - 220 "C

'H NMR(200MHz, CDC1,) : δ 1.46(dd, 3H, 7„ _.n =6.4Hz, J _II.F =24.9Hz),

2.04(s, 3H), 3.96(s, 6H), 4.98-5.26(m, IH), 5.78(s, IH), 6.55-6.62(m, IH), 7.2(brs, IH),

7.45-7.51(m, IH), 8.6()-8.65(m, IH),

8.8()-8.83(m, IH), 13.23(br s, IH)

EXAMPLE 12 Threo 2-(l-acetoxy-2-tluoiO-/ι-propyl)-N-[(4,6-dimethoxypyrimidin -2-yl) aminocarbonyl]-3-pyridinesulfonamide [ Compound No. 11]

2.9 g of the desired product (while solid) was obtained using the same method of

EXAMPLE 5 from 2.3 g of threo 2-( l-acetoxy-2-fluoro-/?-propyl)-3-pyridinesulfon- amide. m.p. : 190 - 192 Xl

'H NMR(200MHz, CDCl,) : δ 1.28(dd, 3H, 7 _H.H =6.4Hz, 7„ _.F =23.9Hz),

2.01(s, 3H), 3.97(s, 6H), 5.08-5.38(m, IH),

5.79(s, IH), 6.49-6.60(m, IH), 7.20(brs, IH),

7.46-7.53(m, IH), 8.64-8.69(m, IH), 8.82-8.85(m, IH), 13.08(brs, IH)

EXAMPLE 13

Erythro ΛT-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(2-fluoiO -l -hydroxy- n- propyl)-3-pyridinesulfonamide [ Compound No. 7]

2.1 g of the desired product (white solid) was obtained using the same method of EXAMPLE 7 from 3.0 g of erythro 2-( l -acetoxy-2-fluoro-/j-proρyl)-N-[(4,6- dimethoxypyrimidin-2-yl)aminocarbonyl]-3-pyridinesulfonamide m.p. : 151 - 153 X2

¹ H NMR(200MHz, CDCl,) : δ 1.37(dd, 3H, J.._ _u --6.2Hz, _H.F =24.8Hz),

3.95(s, 6H), 4.1 1(d, IH), 4.66-4.95(m, IH), 5.57-5.69(m, I H), 5.78(s, IH), 7.33(brs, IH),

7.46-7.53(m, IH), 8.62-8.67(m, IH),

8.79-8.82(m, IH), 12.98(brs, IH)

EXAMPLE 14

Threo JV-[(4,6-dimethoxypyrimidi n-2-yl)aminocarbonyl]-2-(2-fiuoro-l -hydroxy- n- propyl)-3-pyridinesulfonamide.[ Compound No. 8]

0.7 g of the desired product (white solid) was obtained using the same method of

EXAMPLE 7 from l.Og of threo 2-( l-acetoxy-2-fluoro-/7-propyl)-N-[(4,6-dimethoxy- pyrimidin-2-yl)aminocarbonyl]-3-pyridine sulfonamide. m.p. : 173 - 175 "C Η ΝMR(200MHz, CDCl,) : δ 1.48(dd, 3H, y„ _.H =6.3Hz, „ _.F =24.2Hz),

3.97(s, 6H), 4.40(d, IH), 4.90-5.30(m, IH),

5.31-5.55(m, IH), 5.82(s, IH), 7.3(brs, IH),

7.49-7.55(m, IH), 8.58-8.63(m, IH),

8.82-8.85(m, IH), 13.0(brs, IH)

EXAMPLE 15

The herbicidal effect of the compounds of the present invention was tested by the greenhouse test, d e method is as followings.

Pre-emergence test To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with 5 parts by weight of acetone, 1 part by weight of alkylaryl polyglycol ether as emulsifier was added and the solution diluted with water to the desired concenti'ation. 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 concentrat ion of the active compound in the preparation is of no importance, only the amount of active compound applied per unit area being decisive. After three weeks, the degree of damage to the plants was rated in c damage in comparison to the development of the untreated control. The figures denote :

0% = no action (like untreated control)

20% = slight effect

707c = herbicidal effect

100% = total destruction. In this test, the active compounds( I ) according to the preparation examples exhibited a better herbicidal activity against mono- and dicotyledon weeds.

EXAMPLE 16 post-emergence test To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with 5 parts by weight of acetone, 1 part by weight of emulsifier was added and the solution diluted with water to the desired concentration.

Test plants which had a height of 5 ~ 15 cm were sprayed with the preparation of the active compound in such a way as to apply the particular amounts of active compound desired per unit area. The concentration of the spray liquid was so chosen that the particular amounts of active compound desired were applied in 2,000 / of water / ha. After three weeks, the degree of damage to the plants was rated in % damage in comparision to the development of ihe untreated control.

The figures denote :

0% = no action(like untreated control)

20% = slight effect 707 = herbicidal effect

100% = total destruction.

In this lest, the active compounds( I ) according to the preparation examples exhibited a better herbicidal activity against mono- and dicotyledon weeds.

EXAMPLE 17

Fresh-water treatment paddv submerged test

A plastic pot having a surface area of 60 an or 140cm was filled with a small amount of fertilizer, after then, the sterilized paddy soil of puddled state at the depth of 5- cm. Seeds of barnyard grass, umbrella plant, dayflower, monochoria, toothcup, smartweed, and bulrush et al. and perennial nutrition body of fiat-sedge and arrowhead et al., were seeded or planted in surface layer of soil, and pregerminated rice with 2-3 leaves was transplanted one root per pot at the depth of 2cm.

After planting, the pot was watered for a day at the depth of 2cm and the manufactured herbicide was spot-treated on the plant in manner sililar to the field condition (4mg/pot).

Two weeks after treatment, herbicidal effect was measured by the same survey standard as that for field condition.

It is understood that the ahove examples are illustrative but not limitative of the present invention and that other embodiments within the pirit and scope of the invention

will suggest themselves to those skilled in the art.

Tlie following Table 5 represents the formula of active ingredients of the present invention. The following Table 6~8 represents pre- and post-emergence herbicidal effect of active ingredients.

Table 5.

Structures Compound No.

OH

erythro

threo

OH

mixture

OAc

erythro 4

OAc

threo

Structures Compound No.

OAc

tlireo

erythro

threo

mixture

OAc

erythro _j o 3

Structures Compound No.

threo 1 1

mixture 12

Table 6. PRIMARY SCREENING (PADDY SUBMERGED)-Herbicide

Compound DAT* kg ha ECHOR ¹ " SCPJIX' MOOVA'" CYPSE ⁴ ' SAGPY r ) No.

(note) *DAT : Day After Treatment

(l)ECHOR : Bchinochloa crus-galli

P.BEAUV. var. oryzicolo OHWI. : Barnyard grass (2)SCPJU : Scirpus juncoides ROXB. : Bulrush

(3) CYPSE : Cyperus serotinus ROTTB. : Flat-sedge

(4) MOOVA : Monochoria vaginalis PRESL. : Monochoria

(5) SAGPY : Sagittaria pygmaea MIQ. : Arrow head

Table 7. Harmful Effects Test of Herbicides*'

* 1 U'ansplanted rice : 5 DAT treatment after transplanting of 2 leaves rice

survey : Comparison of living body weight after herbicidal treatment

Table 8. Percentage Control for Barnyard grass