JPS60222466A - Herbicidal sulfonamides - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to novel arylmethane and arylsulfamoyl-sulfonylureas that are useful as pre- and post-emergent herbicides. The compounds of this invention and their agriculturally suitable salts are useful as agricultural chemicals such as herbicides.

U.S. Patent Nos. 4.169.719 and 4127.40
No. 5 Ha discloses benzene and thiophene sulfonamide with herbicidal activity.

US Pat. No. 4,435.206 discloses herbicidally active pyridine sulfonamides.

US Pat. No. 4,420,325 discloses benzylsulfonylureas, for example.

European Patent Application No. 87/780 (published on September 7, 1983) by Nissan Chemical Industries is based on the general formula [where A is HX
C, -C, alkyl or optionally substituted phenyl; B and C are independently H1 halogen, NO, C8 alkyl, CO, R, etc.; D is H or C, -C, alkyl and Z is CH or N, and X and Y are methyl, methoxy, etc.].

European Patent Application No. 71, 4 dated February 9, 1983
No. 41 is the formula [wherein Z is CH or N and rxFicn3 or OC
H,-TJ,stYIdCl,CH,,OCH,.

QC,Hll,CH,OCR,,NH,,)OJCH,
.

A'(CHs)! eCH (OCHsjts or C, -
C, alkyl, IR, is H or C no f3, R
6 is H,CM,,OCH,.

C1, Br, NO,, C02B, 1.50. RB, 05
OJ? 4#50, NR, OR11, and R6 is H or C1-C.

is alkyl, R1 is H or CH, Q is O,
S, or SO, and Ql is CR, R, father is O
is disclosed. Also disclosed is its utility as a pre- and post-emergent herbicide and as a plant growth regulator.

European Patent Application No. 79 dated May 25, 1983.
No. 683 is a compound useful as a herbicide or a plant growth regulator [wherein J is /-31-4 Q is o, s or so; R is H or cn; R8 is II, CH,,0CE8. C1, i3r, C02
R.

50, R6,050, R, or 5O1NR, R11; R1 and R8 are independently H or C, -C3 alkyl; R4 is H or CH,; R5 is C, -C, alkyl, CM ,CIf=CH,,C
1l.

CB! 0CII, or CM, C1l, Cl; R6
is C, -C3 alkyl; and R0 is c, -c, alkyl or CF; and R8 and Ro are independently C, -C, alkyl.

The presence of undesirable plants causes substantial damage to useful crops, especially agricultural products that satisfy basic human food and fiber needs, such as cotton, rice, corn, wheat, etc. Due to the current population expansion and resulting food and fiber shortages, improvements in the production efficiency of these crops are needed. Preventing or minimizing partial damage to such useful crops by killing or inhibiting the growth of undesirable plants is one way to improve the efficiency described above.

Killing undesirable plant growth and prohibiting cutting (control)
There are many types of substances that are useful for this purpose. Such substances here are usually called herbicides.

The present invention relates to two novel compounds, agriculturally suitable compositions containing them, and their use as pre- and/or post-emergent herbicides or as plant growth regulators.

1 150, NHCNA± [In the formula, J is p, CM.

/-1o7-tt IIH J-IS/-19 7-201-21 /-22J-23 J-26J-21 /-307-31 L -32 n is 0 and nu is 1; L is CH or O8 Q is C1l or O Q, is O, S or SO; Q, is O or S; R is H or CHa; R1 is H, C, -C, alkyl, Co, R, SO.

NR,, R, or SO! R1 is Hatake; R2 is I or CH; R8 is H or CH; R4 is H or CHa; R is H, CHg, Cl, Br, CO, R,.

50! NR,,R,50. N(OCR,)CH3,50
, R, or NO, and the richness R6 is H, C, -C, alkyl, CO, R, SO.

NR55Rtt or aSO*Rs@Thea') JR7 is H or C1; R8 is CO, RISo, NR1, RI, SO! N(O
CR, )CHge5OvRu or No; R. is H, C, -Cs alkyl or phenyl; R1° is C01R111sS011A'RI@R1y@
SOJ(OCHm)CHg.

501R Nishiki or NO! R11 is H or CH; R is IIeCtRts*SO@NR@@Ry, 50. N
(OCH,)CM,,50. R, 8 or NO;
R1, is MBC0IRHIg501NR1@J? 1ye
50$<OCHm>CM,,50. B1. or NO, and R14 is H or CH, R, is C1-C alkyl; R1 is cl-c, alkyl; R1? is C, -C, alkyl; Rlm is C, -C, alkyl; RII is CD, , C1, Br, NO, , C, -C.

alkylthio or C, -C, alkylsulfonyl; Rv is H, j', C1, Dr, C11, or OCH.

R is H or C, -C, alkyl; R1 is M, OH
, C1-C, alkyl, C, -C.

Haloalkyl, CI-C, alkoxy 7kA/.

cm-cm alkenyl, C,-C6 alkynyl.

C, -C, alkoxyphenyl, C5-C cycloalkyl, C, -c', cycloalkylalkyl, C, -C
-Alkylcarbonyl, C1-C.

Alkoxycarbonyl, benzyl, C, -C4 haμ alkenyl, CI-C, haloalkynyl.

C, -C.alkylcarbonylalkyl, C3-C@alkoxycarbonylalkyl, or haCI-C, cyanoalkyl; Rls is I or CH, = R, 4 is I or CH, R3, is H, CM, or C, II, and R is H or CM; Rtl is H or CH3; R28 is F, C1, Br, OCH,, SCH3°50,
CH,, Co, CF,, So, N(CH3), or os
o.

X is CH3, OCH3, C1, Br, OCH, CF, or 0CHF; Y is c, -c, alkyl, CHJ', cyclopropyl,
CECH,OCR,,QC2H,,CH,OCH3゜N
H,,NHCH,,N(CH,),,OCR,CH,F
, C.F.

SCH,,0CHICH=CH,,0CII,CECH
,OCH.

CR(OCHiH,) or OCF, H; Z is C
H or N; X1VicH1OCH,, OC, II, or t) CF,
H; Yl is O or CH, so X! is CIIBsCtHs or CH,CF; Y
, is OCH,,QC,E,,5CII3. SC, 111
,OCF,B.

SCF, H, CH, or CH, CH, Dechiri;
H3 or OCH,; Y3 is H or CH; provided that: 1) When x is C1 or Brf), Z is CH, and Y is OCH,, QClH,, NHCH,.

A'(CHs) or OCF, H; 2) X or Y
When is OCF, H, Z is cm; 3) RI+ and R6 are not H at the same time; 4) R3 is H
or when other than C1'''CB alkyl, R11 must be H; 5) 7?1! and RIg are not H at the same time; e) R,,
when is other than H, R13 must be H; 7) R1 and R19 are not I at the same time; and 8) when 7 is 1-8 or J-11, R5 is other than H].

Preferred for high herbicidal activity, high plant growth regulating activity, or favorable synthetic simplicity are: 1) of formula l, where R is H and -') A is A-1. Compound.

2) Y is CN6, CIHB, OCH,,0C2H1l,
CH,OCH@.

CE, F or cp; and L is CH.

The compound of 1) above.

3) / is 7-12. /-1417-18,7-19,1
-26 or J-27, the compound of 2) above.

4) R9 is H and X is Clf or OCH.

The compound of 3) above.

S) / is J-BJ-4, J-5 or J-6, Ix is CH or 0CII3; and Y is C, -Ct alkoxy or C, -C, alkyl, the compound of 1) above .

Particularly preferred for reasons of highest herbicidal activity, greatest plant growth regulating activity and/or greatest simplicity of synthesis are: 1,3-dihydro-A'-((4,6- dimethoxypyrimidin-2-yl)aminocarbonyl-1-oxo-
Benzo[C]furan-7-methanesulfonamide melting point 181-184°C (decomposed)! 1.3-dihydro-A'-((4-methoxy-6-methyl-1,3,s-)riazin-2-yl)-aminocarbonyl]-1-oxybenzo[C]furan-7-methanesulfone Amide melting point 175-1113°C (decomposition); -Methanesulfonamido-1,1-dioxide melting point 222-2225°C; A'-((4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-methylbenzo[B ]thiophene-7-methanesulfonamide-
1,1-dioxide melting point 186-187°C; 3[(:(4#6-cymethoxypyrimidin-2-yl)
aminocarbonyl (aminosulfonylmethyl)-1,5
-dimethyl-IB-pyrazole-4-carboxylic acid ethyl ester melting point iso~183°C; and 5-(((4#6-cymethoxypyrimidin-2-yl)
Aminocarbonyl]aminesulfonylmethyl]-1,3
-Dimethyl-1B-pyrazole-4-carboxylic acid ethyl ester melting point 190°C.

Compounds of Synthesis 2.X can be prepared by one or more of the methods described in Equations 1, 2.3 and 4 below.

As shown in Equation 1, compounds of Formula I can be prepared by reacting a shaped sulfonyl isocyanate with a suitable heterocyclic amine. J here,
R and .i are as described above, R1, is C,-Cs alkyl, and Ru is other than H or OH.

Equation 1 % Formula % This reaction is carried out in an inert neutral solvent such as methylene chloride or xylene at 25-100°C for 0.5-24 hours as taught in US Pat. No. 4,127.4os.

and L is 10H,-, and J's R,,R,.

R,,R,,R. , Ro and R1, are C01RIIl
Compounds of formula 1 that are other than 2■
sulfonamides can be prepared by reacting them with the appropriate methyl carbamate of formula V in the presence of equimolar or greater amounts of trimethylaluminum.

Equation 2 The reaction equation 2 is as taught in European Patent Publication No. 84,244 (published July 27, 1983), in a solvent such as methylene chloride under an inert atmosphere.
It is carried out at 25-40°C. The required carbamates are prepared by reacting the corresponding amines with dimethyl carbonate or methyl chloroformate in the presence of a base.

In addition, J is 7-16. /-17, 7-21 and J-22
Compounds of formula 1 where L is -CH,- can be prepared by reacting a sulfonyl carbamate of formula 1 with a suitable amine of formula 2 as shown in equation 3.

Equation 3 %Formula % This reaction is carried out in a solvent such as dioxane at 0.0% as taught in European Patent Publication No. 44.807.
It is carried out at 50 to 100°C for 5 to 24 hours. The required carbame) Vl is prepared by reacting the corresponding sulfonamide with diphenyl carbonate in the presence of a strong base.

Furthermore, the metal compound of formula (1) in which J is other than /-11z/-17, /-21 and J-22 and L is -CH', the sulfonamide of formula It can be produced by reaction with a suitable heterocyclic phenyl carbamate of formula (1) in the presence of a nuclear base such as 1,8-diazabicyclo(s,to:)undec-7-ene (DBU).

Equation 4 This reaction is carried out in an inert solvent such as dioxane at 20-100°C for 0.5-24 hours according to the method taught in European Patent Publication No. 44.807. The required carbamate (2) is prepared by reacting the corresponding heterocyclic amine (2) with phenyl chloroformate in the presence of a base.

I is 7-1, J-2, J-4, J-4, J-5゜J-6
, J-'I, J-8. J-9. J-10. J-11tJ
-26*7-28 and other than J-30, and L is 0
A compound of formula (1) can be prepared as shown in Equation 5. The intermediate chlorsulfonylurea of formula (1) is prepared by treating the corresponding heterocyclic amine carbonate with commercially available chlorsulfonylisocyanate and then reacting with the appropriate phenol of formula (2).

Equation 5 %formula% In the above formula, I and A are as described above.

The reaction shown in Equation 5 is US i Kitsuki 4391°976
It is best done according to the method taught in No.

The intermediate sulfonyl isocyanate of Equation 1 can be prepared by pressing as shown in Equations 6 and 7.

As shown in Equation 6, J is 1-1. Other than J-2゜7-3 and J-30, 7? a'II"('1-('@
The sulfonyl isocyanate of 2), which is alkyl, R11 is other than hydrogen or a hydroxyl group, and L is 10H8-, is prepared by converting the sulfonamide of 2) into xylene by the method of U.S. Patent No. 4.238.621. Ex-butyl isocyanate and a tertiary amine catalyst in a solvent such as diazabicyclo[112]olpy (BAECO'8') (
D#@TKyhx,)ly,! :j! m! It can be produced by reacting at

Equation 6 COCl,/n-BuNCO DABCO,/xylene/hesulfonylinocyanate is the reaction of an (α) sulfonamide in the presence of a base e.g. Also by a two-step process comprising reacting with butyl isocyanate at reflux temperature to synthesize n-butylsulfonylurea, and (6) reacting this compound with phosgene and a tertiary amine catalyst in xylene solvent at reflux temperature. Can be manufactured from sulfonamides.

This method is described by Ulrich and Sayigh) hwt
trMethodsofPrgpaταtiveOrg
anicchemistry.

Volume 1, pp. 223-241 1,4 cadavn pa cpr
ess.

New York, London, W. Forest, ed.
similar to the method taught in .

Alternatively, as shown in Equation 7, a sulfonyl isocyanate of the formula can be prepared by reacting the corresponding sulfonyl chloride, X, with a cyanate salt.

Equation 7 This reaction is expressed in Japanese Patent Publication No. 51-26,816 (Chm Koshiki,
46ag, 85177892g (1976)]+7) in the presence of phosphorus pentoxide and an alkali metal salt such as lithium iodide in an inert neutral solvent such as acetonitrile for 0.5 to 24 hours at 25 to 100°C. .

Another method for making sulfonylinocyanates is shown in Equation 8. When the sulfonamide of 2) is treated with thionyl chloride, the intermediate N-sulfinylsulfonamide X is obtained from K. When exposed to phosgene in the presence of a catalytic amount of pyridine, this gives the sulfonyl isocyanate.

Equation 8 %formula% In the above formula, J is as described above.

The reaction in equation 8 is H, Ulrich, B, Tucker
.

Sayigh A,Sayigh,/,Org,Chem,,34
This can be best done according to the method of e3200 (1969).

I is 7-1-7-11. /-26, /-28 or J-3
The second sulbonyl isocyanate in which Rx+ill712Ct-Cs7ruxy, Rfi is other than hydrogen and hydrogen, and L is O is an appropriate compound of formula 1 as shown in Equation 9. It can be most easily produced by reacting a substituted phenol with chlorosulfonyl isocyanate. This method is described in U.S. Pat. Nos. 419L553 and 4394.153.
Also in Lohaa, ChexEttr, 105.
2791 (1972).

Equation 9 In the above formula, J has the same meaning as above.

As shown in Equation 10, the sulfonamide of 2) has the formula
can be prepared from the corresponding sulfonyl chloride by contacting with anhydrous or aqueous ammonia.

Equation 10 The preparation of NH4OH sulfonamides from sulfonyl chlorides has been widely reported in the literature. See, for example, the following reviews: F. Hawking and J. S. Lawrencet.
The Sulfonamides,”-HoK, Ltt.
wisandCo,.

London, 1950 and E. H. Northery
,”TheSrblfonamidasandAXli
edCompounds, “Rginholdpubl
ischingCorp, NewYork.

1948° The required methylsulfonyl chloride of formula

Equation 11 [where B is Ct or Br; J is /-1-7-11, /-12, /-13°/-14
, /-24,7-2s, J-26*J-2,1,J-3
1 or J-32, t and L is -CMr; and when J is J-26 or J-1+277, Q+ is SO.

] Equation 12 % Formula % (6) [where B is Ct or Br; /FiJ-13, /-16, /-17, /-21 or J
other than -22; L is -CE'] Equation 11 (α) The conversion of an alkyl halide to an isothiouronium salt is
Well described in the chemical literature. For example, T, B, Joh
nson and J.M., Sprague,/.

A, Chern450 (!, 58, 1348 (1936
): 1 bid, , jjl, 1837 and 2439 (19
37) 1tbsd, 61.176 (1939).

In a typical method, a large benzylic monolide is dissolved in a tetratonic solvent such as methanol or ethanol,
Alternatively, treatment with thiourea in a neutral solvent such as methylene chloride or benzene. Completion of the reaction typically takes between 40 and 8
+~24 hours at a temperature of 0°C is required. product salt x
m is separated by cooling and filtration or by removing the solvent by concentration. Salt XM is generally pure enough to be used directly in step (llb)K without further purification.

Equation 11(6) H formation of sulfonyl chloride by oxidative chlorination of isothiouronium salts 1d, J, Am, C to II-bSac.

As described in ot*2s4s(tjas),
It is most efficiently performed according to Johnson's method. That is, a salt of formula xi (B=chlorine or bromine) is dissolved or suspended in water or aqueous acetic acid and treated with at least 3 equivalents of chlorine at a temperature of 5 to 20°C. When using hydrobromide xy+ (B=bromine), it is sometimes advantageous to replace the bromide ions with nitrate ions prior to chlorination by treatment with an aqueous solution of silver nitrate. The precipitated silver bromide is removed by filtration and Solution F is treated as described above. The product sulfonyl chloride is separated by simple filtration or extraction into a suitable solvent such as methylene chloride or n-butyl tetrahydride, followed by drying and evaporation of the combined organic extracts. No further purification of sulfonyl chloride X is necessary.

of the benzylic chloride or bromide of formula -formula x
The conversion of (1) to the sulfonate salt as shown in equation (12α) is well known in the art. For example, G11bar
t,”5ulfonationandRe1atedR
rations”, Intttrttciencep
publishers, New York, 1965, 1
See pages 36-148 and 161-163. formula x
The method for converting the sulfonate salt of (1) to the sulfonyl chloride of formula X is well known to those skilled in the art.

The benzylic bromide of 2M (B=bromine) is expressed by Equation 1
As shown in Figure 3, a suitable methylaryl compound ■ is converted into N-
It can be produced by treatment with promsuccinimide (NBS).

Equation 13 % Formula %) [In the formula, J is J-12, J-13, J-14, J-15, J-1
6, J-IT, J-21, J-22*t-2a#-25
,y-26 or J-27; L is -CHr; R9 is H*F, C1, Br, OCH, and 1 and when J is J-19 or J-23, R11 is H and R88 and R3, are H when J is J-28] The reaction shown in Equation 13 involves refluxing a solution of the acylmethane derivative drug and N-promsuccinimide in a suitable solvent such as carbon tetrachloride. This can be done most easily by heating to a certain temperature.

Free radical catalysts such as azoisobutyronitrile (AIBN) or benzoyl peroxide are commonly used to initiate this reaction. When the bromination is complete, the cooled reaction mixture is filtered to remove the by-product succinimide and the filtrate is concentrated under vacuum. Large benzylic bromides are often obtained in a state sufficiently pure for further reactions.

Otherwise, it can be purified by vacuum distillation or column chromatography.

The benzylic chloride of 2M (L=chlorine) can be most efficiently synthesized by one of two methods well known in the chemical literature. First, benzyl-type chlorides can be prepared from appropriate arylmethane derivatives of formula (1) by reaction with N-chlorsuccinimide (NC5). This reaction is shown in Equation 14.

Equation 14 The reaction of Equation 14 can be carried out in a manner similar to that described for NBS bromination in Equation 13.

J is 1-1. J-2 or 1. In the compound of formula 1 of -3, ring halogenation occurs along with the benzylic type halogenation of equations 13 and 14. Following conversion to the desired sulfonamide 1, subsequent removal of the ring halogen can be accomplished by methods known in the art.

Alternatively, stratified benzylic chlorides can be prepared from the appropriate benzylic alcohol of Formula XV as shown in Equation 15.

Equation 15 % Formula %) The conversion of an alkyl alcohol to the corresponding chloride is a well-known reaction. One of the most common methods involves reacting the alcohol with thionyl chloride, either alone or in the presence of trace amounts of a suitable base. See, e.g., H. Gtlman and/or E. Kirb.
y,/,,4m,Chem.

Soc,, 51.3475 (1929) sH, Gig 籏l and A, p, Ilewlgtt, Rec, Trav,
Chim151e93 (1932) g and M, S, Ne
winan.

J,Am,Chem,Soc,,62t2295(19
40).

The required aryl methanol of formula xv (shown in Equation 16 for the special case of /==7-27) is
It can be prepared by reducing a suitably substituted aryl carboxylic acid of formula XI with diborane in a solvent such as tetrahydroctane.

Equation 16 [wherein Rm, Ihs, RsI and Ql are as defined above].

Although the reaction of Equation 16 is shown specifically for J = 1-27, this reaction also applies if J is 7-16-J-23 or J
-28, and can be applied to ring systems in which L is -C-. For a description of the use of diporan for the reduction of benzoic acid derivatives, see H,C,
Brown, J., Org.

(See 'Agt'IT, *38*2786 (1973).

can be synthesized by reduction of a suitably substituted benzaldehyde derivative of formula XI with sodium borohydride in a solvent such as ethanol.

Equation 17 [where R, AswRu and Ql are the same as above]
.

Although the reaction of Equation 17 is shown specifically for J = 1-27, this reduction also applies to the ring system /-1-7-15, /-1
8,/-19, J-20,/-23,7-2421-2
5#/-26, 7-28.

J-29, /-30, /11 and J-32, where L is -
For a description of the use of sodium borohydride for the selective reduction of aldehydes, see S. ChaikifL and F.BF2.
, 4m, Chum, SOC, a71g122 (1949
)checking.

Aldehydes of Formula X■ can be prepared by the method of Equation 18 by starting with the appropriate nitriles of Formula X■ (shown for the special example of J=1-27).

Equation 18 [where R, Tom, and Q are as described above].

Although the reaction of Equation 18 is shown specifically for J=J-27, this conversion method applies to J-16, J-17, J-2
The reaction shown in Equation 18 can be similarly applied to all ring systems (L=-CH'') other than 1 and J-22.

C0J, Sh, oaf, and C, P, Garg, Tet.
rahmdros Lett, 9 (1959)* and J.
, A., Marahal L.

LHlAndarsgn, and J.F.5chlich.
er, J.

It can be carried out according to the method of Org, Che Den, 35,858 (197G).

Benzoic acid derivatives of formula xw (shown in Equation 19 for the special case of 7=7-27) can be prepared by hydration of a suitable nitrile of formula Can be produced by decomposition.

Equation 19 () % formula %) (6) [In the formula, R, E, and Ql are as described above]
.

As mentioned above, although the reactions in Equation 19 are shown specifically for J = 1-27, these steps are suitable for I = 7-
16. /-1717-21 or 1-22, and can be applied to all ring systems in which L is -C11''.

Equation 19(α) The diazotization and cupric cyanide Katbrinck reaction of Equation 19(α) is organic5ynthesis, C
o11° VOl, page 1.514.

Equation 19(6) A nitrile of formula X is most conveniently converted to the desired carboxylic acid X is hydrolyzed into

The product is typically separated by extraction into an aqueous base solution followed by extraction with a suitable organic solvent such as ether and acidification of the aqueous layer. Regarding this method, R.Wag
nmr and 11. Zook, “5yntticOr
ganicChemistry,”John(l'1l
ey&5ons, Inc., New York, 1G53
．． See page 412.

A method similar to that described in Equation 19 above can be applied to the synthesis of the 7 enol of 2 as shown in Equation 20 (for the special example of J=J-21, shown in .

Equation 20 [In the formula, \R2OsR - and Ql have the same meanings as above]
.

The reaction in equation 20 is the ring system/-1-1-25°J-21
, J-29, J-31 and J-32, provided that L is 0. It can be applied to The diazotization and hydrolysis reactions shown in Equation 2o can be carried out according to the following method: Stgvgntt and Bttutel, J. Am, Ch.
etn, Soc,.

63.311 (1941) rGrillOt and Gor
mlgy, J, Am, Clt, enthSoc, t67
*1968 (1945) g and Mosetttg and 5
tuart, /.

Am, Chem, Soc...! 1.1 (1939).

The required arylamine derivative of formula
It can be prepared directly by reduction of the corresponding nitro compound of formula XX as shown (for example when J=1-27).

Equation 21 [where Rzo*Rut and Q are as described above].

Although reaction 21 in Equation 21 is shown specifically for J==,,J-27, this reduction applies to all ring systems J-1
-32 can be applied. There are many ways to carry out the reduction of aromatic nitro groups to the corresponding arylamine derivatives. One of the more common methods involves treating a nitro compound of formula XX with an excess of stannous chloride, dihydrate in concentrated hydrochloric acid solution at a temperature of 25-80°C.

Other reductions include Hazlet and I) ornfeld, /
, ^Chgrn, SOC,, 66, 1781 (1944
), and West, J., Chetn, Soc., 127
, 494 (1925), using iron powder in a glacial acetic acid solution. For a general review, see Groggs 8, 1
MouthUnitprocastrsInOrganic5
ynthesis,” McGraw-H6llBook
Co., New York, 1947, pp. 73-128.

Many of the substituted aromatic nitro compounds of formula XX (where all ring systems defined in the Summary of the Invention are presented) include:
It can be synthesized by any of several possible synthetic routes known to those skilled in the art.

Intermediate functionalized arylmethane derivatives of formula D[(L=-CH,) and arylmethanols of formula xv(L=-CH()) can also be synthesized by direct synthetic routes known to those skilled in the art. I can do it.

Heterocyclic amines (2) can be prepared by methods known in the literature known to those skilled in the art or by simple modifications thereof. For example, European Patent Application No. 84,224 (1
dated July 27, 983) and F. Brakerc),
/, Ayn, Chgtn, Sac, 69.3072 (1
947) describes a process for the preparation of aminopyrimidines and triazines substituted by acetal groups. Also, South African Patent Application Nos. 825,045 and 825.
No. 671 is particularly suitable for haloalkyl or haloalkylthio groups such as 0CIIdCH,F, OCH.

A method for producing aminopyrimidines and triazines substituted with CF, SCF, H, and OCF, H is described. South African Patent Application No. 837.434 (198
(October 5, 2013) describes a method for the synthesis of cyclopropylpyrimidines and triazines substituted with alkyl, haloalkyl, alkoxy, haloalkoxy, alkylamino, dialkylamine and alkoxyalkyl.・5,6-cyhydrofurone of 2■ where A is A-2 (
2,a-d:l pyrimidin-2-amine and cyclopenta[d]pyrimidin-2-amine, and 6,7-cyhydro-5H-pyrano (2,a-d
] Pyrimidine-2-amine is disclosed in European Patent Application No. 46.
It is described in No. 677. Heterocyclic compounds in which A is A-5 can be prepared as described in European Patent Application No. 73,562. A is A-6
The heterocyclic compound of the formula ■ is disclosed in European Patent Application No. 94
No. 260.

Furthermore, the following literature can be referred to for the general production method of 1-aminopyrimidine and triazine: ○ series book, “The
Chemistry of Mgtaro-cyclicC
”, IntersigncgPub
lishers, Inc., NewYorkatsdL
on-on0 0 Same series glue, /, “pyr” by Brown
1rnid1nea”, Volume 16.

O same series CDE, M, Smolin and so on.

ps-Triazintta by Rappaport
andDerivatives'', Volume 13.

○ F, C, Schaa-f describing the synthesis of triazine
U.S. Patent No. 3.154.547 to gr.
, l'hbffman and F, C9C95chattf
.

J, Org, Chem-*28*1812 (1963)
.

Agriculturally suitable salts of Shikiden compounds are also useful herbicides;
It can be manufactured by many methods known in the art. For example, metal salts can be prepared by contacting a compound of formula I with a solution of an alkali or alkaline earth metal salt with a sufficiently basic anion (eg hydroxide, alkoxide, carbonate or hydride).

Quaternary amine salts can also be made by similar techniques.

Salts of compounds of formula 1 can also be prepared by interchanging certain cations. Cation exchange 2! This can be carried out by directly contacting an aqueous solution of a salt of the compound (for example an alkali metal or quaternary amine salt) with a solution containing the cation to be exchanged. This method is most effective when the desired salt containing the cation to be exchanged, such as a copper salt, is insoluble in water and can be separated by p-filtration.

Exchange may be carried out by passing an aqueous solution of a salt (eg an alkali metal or quaternary amine salt) of a compound of formula I through a column packed with a cation exchanger containing the cation to be exchanged. In this method, the cations of the resin are exchanged for the cations of the original salt and the desired product exits the column. This method requires that the desired salt is water soluble;
Particularly useful are potassium, sodium or calcium salts, for example.

Acid addition salts useful in the present invention can be obtained by reacting the compound of Example 2 with a suitable acid such as p-toluenesulfonic acid, trichloroacetic acid, and the like.

The following examples illustrate methods for making compounds of the invention.

Example 1 Ethyl 5-(chloromethyl)-1,3-dimethyl-IB-vilazole-4-carboxylate S, Gelin et al., J, Hetttrocyclic C
hefn,,16.

1117-20 (1979) *4
-meth)oxycarbonyl-5-(t-hydroxymethyl)
~1.95 ml (26,8 mmol) of thiochloride was added dropwise to 5.3 JF (26,8 mmol) of 1,3-dimethylpyrazole. This resulted in gas evolution and exotherm. The solution was cooled in a water bath.
A solid was given after 0 minutes.

Melting point 81-83℃, HNMR (90MHz, CDC1
, ): δ1.4(t,0CCH,,3#)+2.65(
s, CH,.

3#)+42(s, NCH,, 3B)+4.4(q.

OCH,C,2l-1)i5.2(8,CH,C1,2
H).

This material was combined with the second reaction product (product of 5.0 N of 4-ethoxycarbonyl-5-(1-hydroxymethyl)-1+3-dimethylpyrazole and 1.93 aff of thionyl chloride) and dissolved in dichloromethane. , washed with common salt, dried (MrtSOa) and concentrated to give a solution with a melting point of 81-8.
Obtained solid 10.7.9 at 3°C.

Example 2 5-(((amino)(imino)methylcothiomethyl)-
Ethyl 1,3-dimethyl-1B-pyrazole-4-carboxylate Compound 1 prepared in Example 1 in 200 tnl of ethanol
A solution was prepared under nitrogen from 0.7, P and thiourea &95F. After refluxing the solution for 4 hours, it was stirred at room temperature overnight. The solvent was then removed under reduced pressure. The residue was then masticated with hexane to give a solid 16I (wet weight) with a melting point of 175-180°C.

Example 3 5-Methanesulfonamide-1,3-dimethyl - Compound 14I of the product of Example 2 dissolved in 9Q of water at 5°C
Then, 10 m of chlorine was added dropwise.

The rate of addition was monitored to ensure that the temperature did not exceed 20°C. As a result, a precipitate was formed. The aqueous portion was decanted and the residue was dissolved in dichloromethane, washed with saturated sodium bicarbonate solution, dried (M9SO4) and concentrated. This residue was dissolved in 00 ml of THF. 5 of this THF solution
Add 10 ml of THF and 10 m of HF to the 751 portion cooled to ℃.
1 liter of ammonium hydroxide solution was added. A suspension formed and was stirred for 6 hours. The reaction mixture was filtered and the mother liquor was concentrated under reduced pressure. The residue gave a light yellow solid &O11 after mastication with ethyl acetate-diethyl ether (40:60).

Melting point: 135-138°C, HNMR (90MHz).

d, DMSO): δ1.2(t, CH, I3#)+2.
3(ssCJ*3E)! &8 (8#NCHsa8B);
4.2 (Q#OCH,, 2H) 14.8 (Jl, CIl
, 50. .

2H) +7.1 (bs, NH,, zli).

Example 4 5-((C(4ee-dimethoxypyrimidin-2-yl)aminocarbonyl]aminosulfonyl]-methyl)-
Ethyl i,a-dimethyl-IH-pyrazole-4-carboxylate In a dry flask under nitrogen, the sulfonamide 0.33F from Example 3 and phenyl (4,6-cymethoxypyrimidin-2-yl) Power, (me) 0.35.
9' and anhydrous acetonitrile for 3° were stirred. Then 1,8-diazabicyclo(ato)undec-7-nin, 19% of the solution was added via syringe and the solution was stirred overnight. Then 50 ml of water is added and 1N is added until a precipitate forms.
lIc1 was added dropwise. The suspension was filtered. The filtration residue gave a solid 0.4N after mastication with diethyl ether: mp 190°C IIB (nud:l-le) 1711 and 16
80(C=0)ri"i'HNMR(200MuzeCD
CI, ): δ1.25(t, CH,,3H)+238(
a, CH, #a#)th L80 (8,0CII,,6B)
;λ94 (s, NCH,, aH): 415 (q, OCR
*t2H) 15.23 (s, CIl, 50.+2B):
5. ? 1(g, 6g, CH*lB)+7.35(bs,
NH, IB) and 15L4 (bs, NII, 1li).

Example 5 2,6-dimethylbenzoic acid methyl ester A solution of 10 Jil of 2,6-dimethylbenzoic acid in 221 thionyl chloride was stirred at reflux temperature for 2 hours. Excess thionyl chloride was removed to yield the crude acid chloride as a yellow oil. This intermediate was added to a stirred solution of 4 tnt methanol in 10 18 pyridine at 65-70<0>C. After the addition was complete, the resulting mixture was stirred at room temperature for 2 hours and then poured into 75 d of ice water.

The aqueous layer was extracted four times with 50 g of ether and the combined organic extracts were combined with 59 g of saturated bicarbonate solution.
Backwashed with aqueous hydrochloric acid and water. A pale yellow oil was obtained after drying and removal of the solvent. This is pulp-to-bulb (b
ulbtobulb) distillation (40-50℃, 0.5 bu H
i to obtain pure 2°6-dimethylbenzoic acid methyl ester asJ+ as a colorless liquid: JR (Phil A) 1725crn”gNkl7? (cD
Cls'jδ13(s, 6H), 3.9(8, 3B),
7.0 = '1.4 (m, 311).

Example 6 2.6-bis-(α,α′-bromomethyl)benzoic acid salt 5.09% of the product from Example 5 in 16ml, N
- A mixture of promsuccinimide tt, tp and 0.19 azoisobutyronitrile was heated to room temperature for 1 hour, the solution was cooled to room temperature, filtered, and solution F was concentrated under vacuum and brought to light. An orange oil was obtained. Ethyl-hexane (1:t, V
Treatment with /V) gave pure 2,6-bis(α,α'-bromomethyl)benzoic acid methyl ester 3.02 as a white solid: 411), 7.5(8,3B),.

Example 7 Foruprom methylphthalide The product from Example 6 (zor) was added to 8 ml of concentrated sulfuric acid and the suspension was warmed to about 60° C. for 3 hours. The solution was cooled and poured into ice water. The resulting white precipitate 'eF:if4
was collected, washed well with water, and dried. Pure 7-bromme+luftalide was obtained by recrystallization from acetone.1. Of was obtained as a white powder. Melting point 127.5
-131'C:Ij? (a, 2#), 5.29 (6, 2
#), 7.4 (Broad d.

'1#), 7.5 (broad d, 1ll), 7.6 (d
d, l).

Example 8 l-CC<amino)(imino)methylcothiomethytetrahydrofuran in 10 ff/in Product from Example 7 1. O
The solution of 9 was treated with 0.33 f of thiourea and the S suspension was warmed to reflux temperature for 15 minutes, yielding a viscous white precipitate. The reaction mixture was cooled and filtered. The collected solids were washed with 1-chlorobutane and dried. The yield of pure title compound was 1.2f as a white powder. Melting point 206-2
11°C (decomposed); NMR (f) MSO-d, ) δ4.
8 (s, l/), 5.4 (8°211), 7.6N broad t, 211), 7.73 (broad t, IH), 9
．． 1()゛Load a, IB), 9.23(7”Load s
, 2B).

Example 9 1.3-dihydro-1-oxy-kunzo[C”]F5
A solution of Example product 9.41 in 0'l aqueous acetic acid 77° C. was cooled to 0° C. and treated with 8 ml of liquid chlorine. Following the addition, the mixture was stirred for 2 hours at θ ~ 10'C, filtered,
The solid was washed well with water. The yield of 1°3-dihydro-1-oxo-benzoCC']furan-7-methanesulfonyl chloride was 56% as a grayish solid: mp 103-105.5°C (decomposition): IR (KBr)
1740.1355, 1200 cm-'.

Example 10 1.3-Dihydro-1-oxo-benzo[C°]futhitrahydrofuran Product of Example 9 5.6F in 5Otne
The solution was cooled to 0'C under a nitrogen atmosphere and treated with anhydrous ammonia 1.5-. The resulting suspension was incubated at room temperature for 3
Stir for hours. The insoluble solids were collected by filtration, washed with water, and dried. Yield of the title compound was 3.8F as a white powder.

Melting point 192-195℃; ノR(K#r)3a40℃32
40, 1740, 1130 cm-': NMRs, 4(a
, 2B), 6.7 (Broad 8.2B) 7.5-7.8
(m, 3B).

Example 11 Ran-7-Methanesulfonyl Isocyanate Thionyl Chloride 25-Solid Side A 2° solution of the product of Example 19 was heated to reflux temperature for 18 hours. This reaction solution was cooled to room temperature,
Excess thionyl chloride was removed under vacuum 1 and the resulting residue was treated with 101phos r716F in toluene and 5 drops of pyridine. This mixture was stirred at reflux temperature for 3 hours.

The solution was cooled, filtered under a stream of nitrogen, and the filtrate was concentrated to give 1,3-dihydro-1-oxy-penzo[C°]furan-7-methanesulfonyl isocyanate as an orange oil. The infrared spectrum of this compound is 2240ζ-1
1750(7)-1 showed the stretching properties of incyanate and carbonyl stretching characteristic absorption in 1750(7)-1.

Example 12 1.3-dihydro-#-[(4,6-cymethoxypyridin-2-yl)aminecarbonyl]-r-oxo-benzoCC']furan-7-methanesulfonamide anhydrous acetonitrile 16-solid A solution of 8 mmol of the product of side example 11 was treated with 1.2 F of 2-amino-4,6-cymethoxypyrimidine and the mixture was heated under nitrogen atmosphere for 2 hours.
Heated to 5-50'C. After stirring for an additional 12 hours at room temperature, the suspension was filtered and the collected solids were washed well with hot acetonitrile.

Yield of the title compound as a yellow powder: 1. It was o2. Melting point 181-184℃ (decomposition): JR (KIJr)
1765.1710,162OS1355cm-Otori-,
NMR (t'Dt'l,) δ3.83 (s, 6R), 5
．． 21<8,211), 5.41(a, 2#), 5.7
6 (g.

lH), 7.35 (Poo-s, 1#), 7.5 (m,
IB),? , 'T(m, 2E), 124(broad g,
1! /).

Hereinafter, the present invention will illustrate the present compounds in Table 1-XXiI, but the compounds are not limited thereto. The compounds shown in the table are Examples 1 to 4! It can be manufactured without using the methods described or modifications thereof that are obvious to those skilled in the art.

Preparations Useful preparations of compounds of formula (1) may be prepared in conventional manner. They are powders, granules, tablets, solutions, suspensions, emulsions,
Includes irrigation agents, concentrated emulsions, etc. Many of these can be applied directly. The spray size preparations can be bulked up in a suitable medium and used in spray volumes of a few liters to a few hundred liters/ha. Highly concentrated compositions are primarily used as intermediates for further preparations. Broadly speaking, the preparations may have an active ingredient ratio of 0.1 to 99% by weight, and a) a surface active ratio of 0.1 to 2.
0% and b) at least one solid or liquid diluent from 1 to 99.9%. More particularly, the preparation will contain these ingredients in approximately the proportions shown in Table vi. 5040-841-20 Powder 1-25
70-990-5 Granules and Tablets 1-955-990-15 High Concentration Composition 9
0-990-100-2 Of course, lower or higher amounts of active ingredient than those listed may be present depending on the intended use and physical properties of the compound. A high proportion of surface-active to active ingredients is particularly desirable and is achieved by incorporation into the formulation or by mixing in a tank.

A typical solid diluent is Watkins (IFatkins).
) et al., “Handbook of In5ecticid
eDustl)ilwentsandCarriers
”, 2nd edition, DorlandBo
oks, C'aldwell.

1, Representative liquid diluents and solvents are listed in Marsden
den), “5olventsgrt, ide”, 2nd edition, Interscience Co., Ltd.
, N, Y, ), 1950. 0.14
The following solubility is suitable for concentrated suspensions; concentrated solutions are preferably stable to phase separation at 0°C.

“McCutchttn”sI)etttrgents
andFmwlsi-j'1ersAnnual", 7
/1z7L/Tsudo Publishing (AILu-rtrdpubl
, Corp., N.J.), and Sisel.
ll) and Food, “Ercc31cm
1opgdiaoJ'5urj'aceActiveA
gttnts”, Chemical Publishing Company (C’chemical
Pwbl, C'o, Inc.

#, Y, ) 1964 indicates surface activity and its recommended uses. All preparations are foamed, caked,
Small amounts of additives may be included to reduce corrosion, microbial growth, etc. Preferably, each ingredient should be cleared by the US Environmental Protection Agency for its intended use.

Methods for producing such compositions are well known.

Solutions are prepared by simply mixing the components.

Finely divided solid compositions are produced by mixing and commonly grinding using a hammer mill or fluid energy mill. Suspensions are made by wet milling [see Littler, U.S. Pat. No. 3.06]
No. 0.084]. Granules and tablets may be produced by spraying the active substance onto preformed granular carriers or by agglomeration methods. Reference, J, E, Br0wn 7ri (Br0wn
1nQ), “Agglo-meration”, C'
hemicdlEngineering.

December 4 issue, p. 147 (1967), and Berry (F.
C'hgmcal Engineer's
Hand-book, 4th edition, pp. 8-59, McGraw-Hill, N.Y., 1
963.

For further literature on preparation techniques see, for example: H, A1. Lukes (Lov, z), U.S. Patent No. 3.2
35゜361, No. 6 @ Lines 16 to 71119 and Examples 1O to 410 R, jr/, Luckttnbaugh
), U.S. Patent No. 3.309.192, column 5, line 43~
Column 7, line 62 and Example 8.12.15.39.41.
52.53.58.132.138~140.162~
164.166.167.169-182゜H, Jisin (niysj1L) and E, ytx, Su (Ksualj)
, U.S. Patent No. Z891,855, lines 34166-5.
Column 17 line and Examples 1 to 4゜G, (,', cri:/ri-q:y (Klingman)
Author, “PgedC'ontralasa5cienc-
", Ji'E7-Willie 7n)', e company (Jo
hniP'1leyand5ons.

Inc., N, Y.), 1961, pp. 81-96.

"lr#edControlH" by J, I), y Raya (Fryttr) and S, A, x Huffs (Evans).
andbook” 5th edition, Blackwell Antiquick Publications (Blackwell
5 scientificPublications, 0x
Ford), 1968, pp. 101-103.

/, H. Ljwchanan, U.S. Patent No. &576.834, April 27, 1971, No. 5
Column line 36 to column 7 line 70 and Examples 1 to 4.17.10
6,123-140°E,R,Six-77-(5haffer), U.S. Patent No. 3.560.616, February 2, 1971, No. 3
Column line 48 to column 7 line 26 and Examples 3 to 9.11 to 18
゜E, So7-su (written by Somersl, “Formrbia
tion”, Talk 9son (Torgeson) m “F
ungicides”.

Chapter 1, i6, Acadebatsuku Press (Acade-m
icPress, New York), 1967.

In the following examples, all parts are by weight unless otherwise noted.

Example 13 Aqueous powder 5-[[(4,6-dimethoxypyrimidin-2-yl)
Aminocarbonyl]aminesulfonylmethyl]-1,3
-dimethyl-IH-pyrazole-4-carboxylic acid ethyl ester 80 Sodium alkylnaphthalene sulfonate 2% Sodium ligninsulfonate 2 widths Synthetic amorphous silica 3 Scale kaolinite 13 widths Each component is thoroughly mixed and milled, e.g. in air. Pass through a mill or hammer mill to obtain an average particle size of less than 25 microns, mix thoroughly and pass through a No. 50 US standard sieve (03 opening).
was passed through and then packaged. .

Example 14 Aqueous powder #-((4,6-cymethoxypyrimidin-2-yl)aminocarbonyl)-2,3-dihydro-2-methylbenzo[B]thiophene-7-methanesulfonamide-1
, 1-dioxide 50, Sodium alkylnaphthalene sulfonate, 2 Low viscosity methyl cellulose, 2 Diatomaceous earth, 46 It was made into particles. The product was remixed and packaged.

Example 15 Granule Example (Irrigation Powder of O 5 Width Attapulguide Granules (US Standard Sieve 20-40 mesh, 0.84-(1,42 m)) In a 95% double cone mixer, the surface of the attapulguide granules A slurry of wettable powder containing solid 254 was sprayed on top of 1.
1. The granules were then dried and packaged.

Example 16 3-[[(4,6-dimethoxypyrimidin-2-yl)
aminocarbonyl (aminosulfonylmethyl)-1,5
-Dimethyl-1B-pyrazole-4-carboxylic acid ethyl ester 98.5'1 Silica Aeroglu 0.5 Synthetic amorphous fine silica i, o* Each component is mixed and ground in a hammer mill, Essentially all US standard sieves #50 (opening 0, 3 arms)
A highly concentrated concentrate was produced that passed through. This material could then be formulated in various ways.

Example 17 Powder Example (6) Hydrable powder 54 Pyrophyllite (powder) 954 The water-soluble powder and pyrophyllite diluent were thoroughly mixed,
It was then packaged. This product was suitable for use as a powder.

Example 18 Low concentration granules 1.3-dihydro-#-((4,e-dimethoxypyrimidin-2-yl)aminocarbonyl)-1-oxo-benzoCC")7lane-7-methanesulfonamide 1 The active ingredient was dissolved in the solvent and the solution was sprayed onto the dedusted granules in a double cone mixer. After the spraying of the sputum was completed, the mixer was operated briefly and the granules were then packaged.

Example 19 Aqueous suspension 1.3-dihydro-#-[(4-methoxy-6-methyl-1,3,5-)riazin-2-yl)-aminocardenyl]-1-oxo-benzo[ C'] 7 Ran-7-methanesulfonamide 40 Polyacrylic acid Thickener 0.3 Dodecylphenol Polyethylene glycol 0.54 Disodium phosphate 1 Monosodium phosphate 05 Polyvinyl alcohol 1.0 Width Water 56.7 Width The ingredients were mixed and ground together in a sand mill to give essentially all particles less than 5 microns in size.

Example 20 Aqueous Suspension 5-[:[:(4,6-Simethoxypyrimidin-2-yl)Aminocar? [aminosulfonylmethyl]-1
, 3-dimethyl-IB-pyrazole-4-carboxylic acid ethyl ester 25% hydrated attapulgide 3 crude calcium ligninsulfonate 101 water 62 ml The ingredients were ground together in a ball, side or roller mill to form a solid. The particles were reduced to less than 10 microns in diameter.

Example 21 Solution/V-[(4,6-simethoxypyrimidin-2-yl)
aminocarbonyl)-2,3-dihydro-2-methylbenzo(lthiophene-7-methanesulfonamide-1,
1-Dioxide, sodium salt 5 liters of water The above salt was added directly to water with stirring to form a solution, which was then packaged for use.

Example 22 High concentration 1,3-dihydro-A/-[(4,6-cymethoxypyrimidin-2-yl)aminecarbonyl]-1-oxo-
Benzo[C゛]]furan-methanesulfonamide 99c
6 Silica Aeroglu 0.54 Synthetic amorphous silica 0.5 The ingredients were mixed and ground in a hammer mill so that essentially all passed through a No. 50 US standard sieve (0, 3 openings). It was made into a substance that This concentrate could be further formulated if necessary.

Example 23 Wettable powder 1.3-dihydro-#-[(4-methoxy-6-methyl-1,3,5-)riazin-2-yl)-aminocal]-1-oxy-benzo(( ,') Furan-7-Methanesulfonamide 40 Sodium Lignosulfonate 20 Width Montmorillonite Clay 40 qb Each component was thoroughly mixed, coarsely hammer milled, and then air milled to remove essentially all particles. to a particle size of less than 10 microns. The material was remixed and then packaged.

Example 24 Oily Suspension #-[(4-methoxy-6-methyl-1,3゜5-triazin-2-yl)aminocarbinyl]-2-methylbenzo[B]thiophene-7-methanesulfonamide- 1
, 1-dioxide (35) mixture of polyalcohol carboxylic acid ester and oil-soluble petroleum sulfonate (6) xylene (59) The ingredients were combined and ground in a sand mill to reduce essentially all particles to 5 microns or less.

This product could be used directly, extended in oil or emulsified in water.

Example 25 Powder N-[,(4-methoxy-6-methyl-i,a,5-triazin-2-yl)aminocarbonyl]-2-methylbenzo[73]thiophene-7-methanesulfonamide-1,1 The active ingredients were mixed with the attapulguide and then passed through a polymer mill to reduce essentially all particles to less than 200 microns. The ground concentrate was then mixed with powdered pyrophyllite until homogeneous.

Example 26 Extruded tablet a-[:[(4,e-dimethoxypyrimidin-2-yl)aminocarbonylcoaminosulfonylmethyl)-1,
s-dimethyl-1ll-pyrazole-4-carboxylic acid ethyl ester 25 anhydrous sodium sulfate 10'! Crude calcium lignin sulfonate 5 Sodium alkylnaphthalene sulfonate LE 4 Calcium/magnesium bentonite 59 The ingredients were mixed, hammer milled, and then warmed with water at about 121 °C. Extrude this mixture into a cylindrical shape with a diameter of about 1 to 3+ u,
This was cut into pellets of 3 lengths. This could be used directly after drying, or the dried pellets could be ground and passed through a No. 20 US standard sieve (0.84y opening).

The granules remaining on a No. 40 US standard sieve (0.42u opening) were packaged for use while circulating under the sieve.

Example 27 Solution s-[[:(4,6-Simethoxypyrimidin-2-yl)aminocal is nylcoaminosulfonylmethyl)-1,
3-dimethyl-IM-pyrazole-4-carboxylic acid ethyl ester 54 Dimethylformamide 95 Applications The compounds of the present invention can be used in areas where complete extermination of all plants is desired, such as near fuel storage tanks, around ammunition depots, and in industrial storage. It is an active herbicide with utility for broad spectrum pre- and/or post-emergent weed control in areas, parking lots, amphitheaters, billboard areas, highways, and railroad areas.

The application rate of the compound of the present invention depends on the type of weed to be exterminated,
It is determined by many factors, including weather and climate, formulation used, method of application, amount of foliage present, etc. Generally speaking, the compounds should be applied in an amount of about 0.05 to 5K47 ha. This lower application rate is useful for use in light soils and/or soils with low organic matter content, or for conditions where only short-term persistence is required.

The compounds of the invention may be used with other commercially available herbicides such as triazines,
It may also be used in combination with triazole, uracil, urea, amide, diphenyl ether, carbamate and bipyridinium types. This compound can also be used in combination with mefluidide.

The herbicidal activity of this compound is demonstrated in a number of greenhouse tests. The test method and results are as follows.

Test A Kingfisher (DigitaliaIff), Inubi x (E
chi-nochloacruagalli), oat (Avana fatua), sickle pot (5ic
hlrpot) ((,'assiaobtuaifol
ia), Asaga, t (IpomoeaIll), Onamomi (Xanthiumpensylvanicutn)
, sorghum, corn, soybean, sugar beet,
Rice, wheat, cotton seeds and purple hummus ((,
'yperws rotundua) tubers were planted and pre-emergent treated with a test compound dissolved in a solvent harmless to the plants.

At the same time, these crops and miscellaneous species were subjected to post-emergence treatment by application to 7 leaves of soil. The timing of this treatment ranged from 2 to 18 ctn in plant height. The treated and control plants were then kept in the greenhouse for 16 days, after which all species were compared to the control plants and the response to treatment was visually assessed. The ratings summarized in Table A range from 0 = no damage to 10
= It is based on a numerical scale that leads to complete extinction. The letter symbols that follow have the following meanings: C' = yellowing or ring E - germination inhibition G = growth retardation, and H = shadowing effect The test compounds in the results table are as follows: Test B After germination two round pots (diameter 25 m, depth 125 cm) were filled with sandy loam of fF'oodstown. In one pot, there is black grass (black-
grass) (Alpecrbrwsmysuroid
es), sugar beet, Hamas'r"(C'ypgr
1Lsrotrbndxs) Tuber, Siclebot ((,
'assiaobtusifolia), velvet leaf (Abutilonth, eophrasti),
Oilseed rape (Brassicanopus) and Setaria faberii were planted. Other pots include wheat, cotton, rice, corn, soybean, oat (Avenafatua), Japanese snail (Xan-tiumpensyLsantcumr),
Morning glory (Ipomogahederacea), Johnson Gras, x (Sorghumhalepense)
and Echinochloacrrbsga
lli) was planted. Plants were allowed to grow for approximately 14 days and then post-emergent sprayed with a compound dissolved in a solvent that is harmless to the plants.

Pre-germination Two round pots (diameter 25-1 depth 12.5cr++)
filled with sandy loam soil in Utuzu Town. One pot contains blackgrass, sugar beet, hummus r, crabgrass, sicklepot, and teawged.
, Datura, Velvet Leaf, Brassica,
and Physcomitrella sinensis were planted. In other pots, wheat,
Cotton, rice, maize, soybeans, oats, Japanese fir, morning glory, Japanese millet, and Japanese millet were planted. Two pots were pre-emergent sprayed with a compound dissolved in a solvent that is harmless to the plants.

The treated and control plants were kept in the greenhouse for 28 days and then all treated plants were compared to the control plants in Test A.
Plant responses were evaluated visually using an evaluation system as described in .

Response evaluations are shown in Table 8. The data indicate that some of the test compounds are extremely useful in selectively controlling violets in crops such as wheat, soybeans, and cotton.

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Claims (1)

[Claims] 1, 2〇1 1SO, NHCNAI [In the formula, outside is 0 or 1, and the number is CH, or O; Q is CH, or O; Ql is O, S, or SO, and Q! is O or S and R is H or CH; R1 is H, C, -C, alkyl, Co, RI. SO, NR, R, or SOtR; R1 is H
or CH,; R, is H or CH Hatake; R4 is H or CH,; R3 is Ii, CIIB, Cl, Br, CO, R,. 5O7iR,,R,,,SOt/v(OCR,)CM,
, 501R1° or NO; R6 is H, C, -C, alkyl, CO, R. S()JRlaRty or SO,R1,; R7 is H or CM; R8 is “zRis*SO$RtsRsts5OJ(OC
H,) C11, SO, R1, or NO; R・
is HlCr-Cs alkyl or phenyl; Rlo is CO, R, , So, NR111R, , 50
Direct (OCI!,) CH,, SO, R, or NO, and luck RII is g, 9 is CHa; RI! II, C01R1,,50鵞NR,6R,TE,
So, N(OCIIJCH,, 50, R, or NO,
and black RIs are H, CO, Rls, SO, NR, eR
, ), So, N(OCH,) C11,, 50, R, or NO, and RI4 is H or CH3; RIII is c, -c, alkyl; R, . is C, -
C, alkyl; Rn is C, -C, alkyl; R1, is C1-C! is alkyl; R1m1 is C'E@, Cl, Br, NO,, CI-C. Alkylthio or C, -C, alkylsulfonyl, and R9 is H, F, C1, By, C1l, or OCH; R11 is H or C, -C, alkyl, and R1! KeH
, OH, Cl-Ca alkyl-C1-Ce haloalkyl, CI-C alkoxyalkyl, C, -C, alkenyl, C@alkynyl, Cl-C6 alkoxyphenyl, C5-cm cycloalkyl, C4-C?cyclo Alkylalkyl, C, -C alkylcarbonyl, C, -
C6 alkoxycarbonyl, benzyl, C3-C4 haloalkenyl, CI-C11 haloalkyni λ, Cm-Cm
Furkylcarbonylalkyl, ca'-06 alkoxycarbonylalkyl, or haC, -C, cyanoalkyl; R3 is H or C1l, and 8 R8 is H or CH; R is H, CH, or C, H, 'l:, S; R9 is H or CHl; R4 is H or CHs; R3, is F, Cl, Br, 0CIIB, SCH,. 50,C1l,,CO,CH,,So,N(CH,),
or 050, CH, (-IA-2'A-3; X is CH3,0CII, , C1,Br,0CIIICF
B or 0CHF; Y is C, -C, alkyl, CM, F, cyclopropyl,
C3CH,OCH,,QC,B! ,C1lρCH,,H
E,,NECH,,N(CH,),,OCR,C1l,
F,CF,,SCH,,OCH,CC11=C,,0C
II, C Mi CHXOCH. CR (OCH, CH, ), or 0CFJI; Z is CM or N; x is CH,, OCH,, QC, lll1 or OcF,
H-C' is present; Y is O or CH; X is C11, C, H, or CH, CF, and Y
t is OCR,,QC,If,,SCH,,SC,Hll
. OCF*U, SCF, H, CH, Straddle Cll, Cll,
'X is CH, or OCH, and Y is H or CH; However, - 1) When x is C1 or Br, Z is CHC, and Y is 0CE3. QC, H,, NHC horse. #(CHs)* or OCF, II and 2) x or Y
When is OCF, H, Z is CM; 3) R3 and R6 are not H at the same time; 4) When R6 is other than H or C, -C, alkyl, R5 must be H; 5) R1! and R4 are not H at the same time; 6) when R is other than H, R33 must be H; 7) R5 and R111 are not H at the same time; and 3) /
is J-8 or J-11, R1 is other than H]. 2. The compound according to claim 1, wherein R is H and A is 4-1. &Y is CE,,C,Hll,OCH,,QC,H,. CHlOCH,, CH, F or CF, and L is C
H. The compound according to claim 2, which is 4J is 1-12. J-14, J-19eJ-26 or J
-27. The compound according to claim 3, which is -27. s, R2O is H, and X is CH or OCH. The compound according to claim 4, which is 6, 7 is J-1, J-4, J-5'51 is /-6, Ix is CM or OCH, and Y is CI-C,
3. The compound according to claim 2, which is alkoxy or C,-C,alkyl. 7.1.3-dihydro-#-(:(4,6-cymethoxypyrimidin-2-yl)aminocarbonyl-1-oxobenzo[C]furan-7-methanesulfonamide) Claim 1 Compound described in Section 8.1t3-dihydro,N-[(4-methoxy-6-methyl-1,1,5-triazin-2-yl)aminocarbonyl]-1-oxo-benzo[C]furan-7 -methanesulfonamide, according to claim 1. 9, #-((a,e-dimethoxypyrimidin-2-yl)aminocarbonyl)-2,3-dihydro-2-methylbenzo [B] The compound according to claim 1, which is thio7ene-7-methanesulfonamide 1,1-dioxide. 10, #-((4-methoxy-6-methyl-1°g, s
2. The compound according to claim 1, which is lyazin-2-yl)aminocarbonyl]-2-methylbenzo[B]thiophene-7-methanesulfonamide-1,1-dioxide. tt, 3-[:[(4,6-Simethoxybilimidino-2-yl)aminocarbonylcoaminosulfonylmethyl)-r,s-dimethyl-IB-pyrazole-4-carboxylic acid ethyl ester. A compound according to item 1 in the range 1. 1λ5-(((4we-dimethoxypyrimidin-2-yl)aminocarbonyl]aminesulfonylmethyl)-1
, 3-dimethyl-II nopyrazole-4-carboxylic acid ethyl ester fj. The compound according to claim 1. l & an effective amount of a compound according to claim 1 and at least one of the following compounds, i.e. a surfactant, a solid or liquid diluent, suitable for controlling undesirable plant growth. composition. 14. for controlling undesirable plant growth, comprising an effective amount of a compound according to claim 2 and at least one of the following compounds: a surfactant, a solid or liquid diluent; suitable composition. 15. suitable for controlling undesirable plant growth, comprising an effective amount of a compound according to claim 3 and at least one of the following compounds: a surfactant, a solid or disintegrating diluent; composition. 1a suitable for controlling undesirable plant growth, comprising an effective amount of a compound according to claim 4 and at least one of the following compounds: a surfactant, a solid or liquid diluent; composition. 17. for controlling undesirable plant growth, comprising an effective amount of a compound according to claim 5 and at least one of the following compounds: a surfactant, a solid or liquid diluent; suitable composition. 18. for controlling undesirable plant growth, comprising an effective amount of a compound according to claim 6 and at least one of the following compounds: a surfactant, a solid or liquid diluent; suitable composition. 19. A method for controlling undesirable plant growth comprising an effective amount of a compound according to claim 7 and at least one of the following compounds: a surfactant, a solid or liquid diluent. composition suitable for. 20. for controlling undesirable plant growth, comprising an effective amount of a compound according to claim 8 and at least one of the following compounds: a surfactant, a solid or liquid diluent; suitable composition. 21. for controlling undesirable plant growth, comprising an effective amount of a compound according to claim 9 and at least one of the following compounds: a surfactant, a solid or liquid diluent; suitable composition. 22. for controlling undesirable plant growth, comprising an effective amount of a compound according to claim 10 and at least one of the following compounds: a surfactant, a solid or liquid diluent; suitable composition. 2 & an effective amount of a compound according to claim 11 and at least 1 g of a compound suitable for controlling undesirable plant growth, i.e. a surfactant, a solid or liquid diluent; Composition. 24. for controlling undesirable plant growth, comprising an effective amount of a compound according to claim 12 and at least one of the following compounds: a surfactant, a solid or liquid diluent; suitable composition. 2. A composition suitable for controlling undesirable plant growth, comprising applying an effective amount of a compound according to claim 1 to the area to be protected. 2. A composition suitable for controlling undesirable plant growth, comprising applying an effective amount of a compound according to claim 2 to the area to be protected. 2. A composition suitable for controlling undesirable plant growth, comprising applying an effective amount of a compound according to claim 3 to the area to be preserved. 2. A composition suitable for controlling undesirable plant growth, comprising applying an effective amount of a compound according to claim 4 to the area to be protected. 2. A composition suitable for controlling undesirable plant growth, comprising applying an effective amount of a compound according to claim 5 to the area to be protected. 30, an effective amount of the compound according to claim 6,
A composition suitable for controlling undesirable plant growth, comprising applying it to the area to be protected. 31, an effective amount of the compound according to claim 7,
A composition suitable for controlling undesirable plant growth, comprising applying it to the area to be protected. 32, an effective amount of the compound according to claim 8,
A composition suitable for controlling undesirable plant growth comprising applying it to the area to be protected. 33, an effective amount of the compound according to claim 9,
A composition suitable for controlling undesirable plant growth, comprising applying it to the area to be protected. 34. A composition suitable for controlling undesirable plant growth, comprising applying an effective amount of a compound according to claim 10 to the area to be protected. 35. A composition suitable for controlling undesirable plant growth, comprising applying an effective amount of a compound according to claim 11 to the area to be protected. 36. A composition suitable for controlling undesirable plant growth comprising applying an effective amount of a compound according to claim 12 to the area to be protected.