JPS5818358A - Herbicidal indole sulfonates - 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]

The present invention relates to novel N-(heterocyclic aminocarbonyl)indol sulfonamides useful as pesticides, particularly herbicides. Canadian Patent No. 74 No. 920 (issued December 6, 1966, Upjohn) discloses that 3-(alkylcarbamoylsulfamoyl)-1-γ-rukylindole-2-carboxylic acids and esters (1) (i) a sedative, R and R2 are auto-04 alkyl, and R1 is H or C,-C4 alkyl;
It is disclosed as a diuretic, an antibacterial agent and/or a sunburn IE cream. U.S. Pat. No. 4,124,405 discloses that the formulas R3 and R6 are independently hydrogen, fluorine, chlorine, bromine, iodine, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, nitro, trifluoromethyl , cyan, CHsS(0)n- or CI(,CH25(0)
n-; R4 is hydrogen, fluorine, chlorine, bromine or methyl; R5 is hydrogen, fluorine, chlorine, bromine, methyl or methoxy; R7 is hydrogen, fluorine, chlorine, bromine, 1 to 2 alkyl of carbon atoms or alkoxyteary of 1 to 2 (f6+) carbon atoms; R8 is hydrogen, methyl, chlorine or bromine; R9 and RIG are independently hydrogen, methyl, chlorine or bromine; -17- W and Q is independently oxygen or sulfur; n is 0.
1 or 2: X is hydrogen, chlorine, bromine, methyl, ethyl, alkoxy of 1 to 3 carbon atoms, trifluoromethyl, CH3S-'t
or CR30CR2-; and Y is methyl or methoxy, provided that a) R
When s is other than hydrogen, R3, R4, R6 and R7
at least one of is other than hydrogen, and R3, R4
, R6 and R7 must be hydrogen; (b) Rs is hydrogen; and R3, R4, R6
and when all of R7 are other than hydrogen, R3, R4
, R6 and R7 must all be chlorine or methyl, and (c) when Rs and R7 are both hydrogen,
At least one of R4, Rs 'E or R6 is water 18
- teaches compounds or agriculturally suitable salts thereof that must be pure and useful for controlling weeds in wheat; French Patent No. 1.468.747 discloses the following p-substituted phenylsulfonamides useful as anti-diabetic agents: where R is H1 halogen, CF3'J alkyl. Logemann et al, Chem, Ab.
, 53°18052g (1959) discloses a number of sulfonamides, such as uracil derivatives and having the formula, and R1 is hydrogen- or methyl. Rat (25mg/10
Compounds in which R is butyl and phenyl were the most potent when tested for hypoglycemic effects in oral administration of 02). Other compounds had low potency or were inactive. Wojciechowski+ J, Aeta, P
o1on, Pharm. 19, p121-5 (1962) [Chem Ab,. So, 1633e] describes the synthesis of sulfonamides of the formula %. Based on similarities to known compounds, the authors predicted hypoglycemic activity for the compound. Dutch Patent No. 121,788 (September 15, 1966)
(1) where R1 and R2 can independently be alkyl of 1 to 4 carbon atoms, and R3 and R4 are independently hydrogen, chlorine or 1 to 4 carbon atoms. The preparation of compounds of and their use as general or selective herbicides is taught. The compound of formula (g) 1 in which R is pyridyl, -21- and its use as an antidiabetic agent are disclosed in J.
Reported in Drug, Res, 6.123 (197't). U.S. Patent Application No. 244.172 discloses that in the formula
1C(0)CC13,5OzRos C(0)Rs
or CO₂H, R2 is H or C1-C4 alkyl, and R3 is Hl
C, -c, alkyl, C1l or Br, 22- R4 is H, cl-e, alkyl, cyanoethyl, C3-
C6 cycloalkyl, benzyl, phenyl (substituted with C1 NO2), or C(O) R, R5UC1-C4 alkyl or cl-c4 alkoxy, R(fd, ct C4 alkyl, C1- 04 alkoxy or N R7RB, ■ t7 and R8 are independently C, -C2 alkyl, R9 is H, CHst or OCR3, ■ 1.. is C
1-c4 alkyl, 23-, X is Cf (3t or OCH3, Y is HXCH3, OCH3, OCR2CR3,0CH2
CFll, C1, CH20CH3, CHI OCR2C
Hs or CF3, Y”td, HXCH3,0CI (3, C1 or O
CI (20H. and Z u C) (XNXCCH!, CCH2CH3, CC
Discloses herbicidal compounds and agriculturally suitable salts of which are H2CH, C1, CCIXCBr or CF. The presence of undesirable plants causes substantial damage to useful crops that meet human basic plant requirements, especially agricultural products and fiber requirements, such as cotton, rice, corn, wheat, etc. Current population growth and associated global food reserves demand production efficiency from these crops. Preventing or reducing the loss of a portion of a highly valuable crop by killing or inhibiting its growth is one way to improve this efficiency. It's a method. 7 Volatile substances are available that will kill or inhibit the growth of unwanted plants. Such substances are commonly called herbicides. However, there is a need for more effective herbicides. The present invention relates to novel compounds of formula (1), (2) and (2), suitable agricultural compositions containing them, and their use as general and selective, pre- or post-emergent herbicides. Formula % Formula % In the formula, R is HXct-04 alkyl, (CR2)m C02R
11, CH, QC, R5, S 02 RIG, CHO,
So□NR11R12, CR2N (CH3h '! or CH20CH,; R1 is H, cl-c, alkyl, C02R6, C(0)NR7Rs, C(0) Rlo
XS 02 R16X or S o, NR11R1
2; R2 is! (, C, -C3 alkyl or S 02 'c
6H5; R3 is I(XF, C1, Br, auto-03 alkyl, c
, C3 alkoxy sulfate NO2; R4 is ■,
C1 or Br; R, is H or CH3; R6 is C, -C, alkyl, 0s-C4 alkenyl, C
H2CR2C1 or CHz CR20CHs;
R7 and R8 are independently H or cl-04 alkyl, with the total number of carbon atoms being less than or equal to 4; R9 is H or C,-C3 alkyl; RIG is c
t-C3 alkyl; all and R1□ are independently C1-03 alkyl, with the total number of carbon atoms being less than or equal to 4; m is 0.1 or 2; X is CHs or OCH, Y is CI(3,0CI-1,,oc,)Il, CH2Q
C) 13, CI, HXC2H, or N(CH3)2
and 2 is CH or N, provided that 1) When R2 is SO2C, R5, R1 and R
is H or C1-C5 alkyl, and 2) Y is C
When I, 2 is C) I, 27- and when m is 0, R9 is C, -C, alkyl. Preferred compounds because of their higher herbicidal activity and/or easier synthesis are as follows: (1) R, or HXC, -C3 alkyl, CO, R,
, C(0) NRt Rs , S 02 NRII R
12 or S o, R,. (2) Preferred compounds of (1) wherein R and R are H; (3) Preferred compounds where R is H or CH. (2)
' compound, (R1 is Hyc6□CH3,5O2CH3 or S
The preferred compound (3) is O,N(CH3), (
5) Y is CR3, OCH3, QC2Is, CHlQ
Preferred compound (4) which is CH328- or CI, (6) R is ■, c t-c , , alkyl, (CR2)mC02R
9,5ozRto or S o2NRII R1l! and a general range of compounds of formula (7) in which R5 is (7) preferred (6) in which Rs and R4 are H
(8) Preferably (7) where R2 is H or CH3
compound, (9) R is H, Ck13 or (CI(z)-COz
-(Cs-Cm alkyl), and (10) Y is CH3,0CHs, QC2R5, CH
Preferred compound (9) which is 2QCR3 or CI
Particularly preferred compounds, because they have the highest herbicidal activity and/or are most preferably easy to synthesize, are: 2
9-l)aminocarbonylcoaminosulfonyl]-1-methyl-1H-indole-2-carboxylic acid, methyl ester, 3(((4,6-dimethylpyrimidi/-2-yl)aminocarbonyl)aminesulfonyl]-1 -methyl-1H
-indole-2-carboxylic acid, methyl ester, 3-[((4-methoxy-6-methylpyrimidine-2-
yl)aminocarbonylcoaminosulfonyl]-1-methyl-1i(-indole-2-carboxylic acid, methyl ester 1.5-[C(4,6-cymethoxy1.3.5-triazid/-2-yl) aminocarbonyl]aminosulfonyl]-1-methyl-1H-indole-2-carboxylic acid,
Methyl ester, 5-(C(4,6-simethoxy1.3.5-triazin-2-yl)aminocarbonyl]aminosulfo-30
-Nyl]-1-methyl-I H-indole-2-carbonyl'47, methyl ester, 3-CC(4-methyl-6-medoxy1.3.5-triazin-2-yl]aminocarbonyl]amine sulfonyl]-1-methyl-1'H-indole-2-carvone, methylnisder N-((46-cymethoxypyrimidin-2-yl)aminocarbonyl-3-methyl-1H-indole-2-
Sulfonamide, N-((4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-6-methyl-1 if-indole-
2-Sulfonamide, m-((4-methyl-6-medoxypyrimidin-2-yl)ami7carbonyl]-3-methyl-1 fI-indole-2-sulfonamide, N-((4.6 -Simethoxy1,3.5-triacyar2-yl)aminocarbonyl]-3-methyl-114-'fthonyl-2-sulfonamide, N-((4,6-cymethoxy1.3.5-)lyazine-2- yl)aminocarbonylcou-3-methyl-1H-1ndole-2-
Sulfonamide, N-((4-methyl-6-medoxy-1,3.5-triazin-2-yl)aminocarbonylcou-3-methyl-1H-indole-2-sulfonamide, 3-[((4.6 -cymethoxypyrimidin-2-yl)
Aminocarbonyl]aminesulfonyl]-1H-indole-2-carboxylic acid, ethyl ester, 3-[((46-cymethoxy1,3.5-triazin-2-yl)aminocarbonyl]aminesulfonyl]-1H-indole- 2-carboxylic acid, ethyl ester, 3-([(4-methoxy-6-methyl-1.3.5
-triazin-2-yl)aminocarbonylcoaminosulfonyl]-I H-indole-2-carboxylic acid, ethyl ester, 3-(((4-methoxy-6-methylpyrimidine-2-
yl)aminocarbonyl]aminosulfonyl]-1H-
Indole-2-carboxylic acid, ethyl ester, 3-[[(4.6-dimethylpyrimidine-2-inoliaminocarbonyl]aminosulfonyl] - 1 H-indole-2-carboxylic acid, ethyl ester. Formula A general method for producing the compound of formula (1) is shown by the following reaction formula (1): (1) 33--More specifically, the compound of the present invention of formula I is prepared by combining a heterocyclic amine of formula V and a chlorosulfonyl isocyanate. These compounds are produced in situ in a convenient case and used without isolation in the synthesis of compounds of formula I. , an aminocarbonyl sulfonyl chloride of formula (1) is contacted with an indole of formula (1), preferably in the presence of a Friedel-Krach catalyst, to produce a herbicidal indole sulfonamide of formula I. The reaction mixture is dissolved or suspended in an active organic solvent such as, but not limited to, dichloromethane, nitromethane, nitropropane, tetrahydrofuran or nitroethane.
Maintain at 0°C. When tetrahydrofuran is the solvent, the preferred temperature range is -80°C to -50°C; for nitromethane, the preferred range is -20°C to 0°C. 1 equivalent of chlorosulfonyl isocyanate alone or when tetrahydrofuran is not the solvent,
It is dissolved in a solvent and contacted with the amine at a rate that maintains the reaction temperature within the preferred range. The reaction proceeds rapidly and the reaction mixture is brought to the desired temperature range by 0.1
Maintain for ~1.0 hours to ensure complete formation of intermediate 1'5o Compound 2 is then dissolved in an equimolar amount of indole or a solvent at a temperature within the preferred range for the solvent used. From this point on, the reaction conditions used will depend on the nature of the substituents on the virole base of the indole nucleus.
For the reaction with the -C3 alkyl indole (2), a Friedel-Krach catalyst can be added, if necessary, at a temperature within a preferred range. Friedel-Crafts catalysts are
dRe1ated Reactions”G, A
, edited by 01ah, Interseience Pub
It is broadly defined in Chapter 1, New York, 1963. Preferred catalysts are acidic halides, typically aluminum chloride and aluminum bromide, which have an electron-deficient central metal atom that can accept or take electrons from basic reagents. More preferably, aluminum chloride (ID'!r) is used in catalytic amounts, the exact amount of which will be clear to those skilled in the art.The reaction mixture is warmed to ambient temperature and the reaction is completed, usually at 0. Maintain in an inert atmosphere for 5 to 24 hours. Tetrahydrofuran and nitroethane are preferred for these reactions. , indole which is R5■
For the reaction with, an equimolar amount of Friedel-Krach catalyst, preferably aluminum chloride, is added to the reaction mixture at this point. The reaction mixture is warmed to ambient temperature and then heated to ambient temperature under an inert atmosphere. The temperature is maintained at the boiling point of the solvent, preferably nitromethane, at 1. The reaction proceeds to completion within 0.5 to 24 hours. Generally,
Higher reaction temperature and shorter reaction time (05-4
time) gives the highest yield. In all cases,
Intermediate (1) is preferably prepared in the same solvent in which the reaction with indole (2) is carried out. Compounds of the invention of formula (3) can be isolated by partitioning the reaction mixture between an aqueous alkali and an organic solvent such as dichloromethane or chloroform. The product is soluble in the aqueous phase and can be precipitated from it after separation of the layers by adding a slight excess of acid, such as acetic acid or f2. If the product does not precipitate upon acidification, it can be isolated by extraction into an organic solvent such as dichloromethane, nitromethane or molten ethyl acetate and then evaporating the solvent. When the reaction is carried out in a water-immiscible solvent, such as dichloromethane or nitromethane, isolation of the product involves contacting the reaction mixture with water, followed by phase separation, and further displacing the product in an organic solvent, e.g. This is best accomplished by extraction into dichloromethane, nitromethane, nitroethane or ethyl acetate. Evaporation of the organic solvent yields the crude product of formula I. Purification of the reaction product can be achieved by grinding using a suitable solvent.58
-P4 ;! 'i' (for crystallization chromatography,
[5″-ro by re-squeezing. Hand 1111, which is generally used in the anti-LC type, has R1 of Co
2R6, C(0) RIn XS 02 RIO or S 02 NRII R12, and I recommendation is ■■
It is also 1dct C3 alkyl, or R,
is H dimension or auto-C4 alkyl, and R2 is auto-C4 alkyl.
Formula 1 which is C3 alkyl also fd S 02'C6H5
It is suitable for the production of indole sulfonamides. R
1 is H, formulas I and II (R-
4,=)I) isomeric products are generally obtained by these methods, and are obtained by column chromatography, preparative high pressure 1 (medium pressure chromatography, or similar methods). Indole sulfonamides of formula I, in which R1 is C(0)NR7R, are preferably derived from the corresponding compounds in which R1 is C02CR3, to anti-Lr, 1, as in formula (2):
It is produced by reaction with a dialkylaluminium-N-alkylamide derivative. This method is disclosed in unexamined European Patent No. 7687, filed February 6, 1980. R, is Hl or C,-C4 alkyl, and R2
The indole sulfonamide of formula (3) in which is H is preferably such that R2 is S 02C6 as shown in reaction formula (3).
It is produced by alkaline hydrolysis of the corresponding compound which is H5. The reaction is carried out in an excess of aqueous alkaline, preferably in the presence of a water-miscible co-baking medium, such as dioxane or tetrahydrofuran, at temperatures ranging from ambient temperature to the reflux temperature of the solvent mixture used. -ru. 1-2
After 4 hours, the reaction mixture is diluted with water and acidified with aqueous hydrochloric acid at 0-5°C to precipitate the product. The compound of the present invention of formula
) can be manufactured by one of two methods. -41- VI V■ 42- As shown in reaction formula (4), the compound of formula (1) can be prepared by reacting the amino-heterocyclic compound V with the appropriately substituted sulfonyl isocyanate (2). The reaction is best carried out at ambient temperature in an inert aprotic organic solvent, such as methylene chloride to acetonitrile, or tetrahydrofuran. Method of addition (
Although not heavily loaded, it is often preferred to add a solution of sulfonylisocyanate I to a stirred solution of amino-heterocycle V. This reaction is generally exothermic. In some cases, the desired product is insoluble in the reaction medium and the product which is soluble in the reaction medium is crystallized from it in pure form by evaporation of the solvent, the residual solvent, e.g. 1-chlorobutane. , trituration with methylene chloride or ethyl ether, and filtration. The intermediate sulfonyl isocyanate of formula VI combines the corresponding sulfonamide of formula
It is prepared by reacting butyl isocyanate in a solvent such as xylene at reflux temperature in the presence of a non-nucleophilic group such as 1,4-diazabicyclo(2,2,2)octane. Ru. 1 ton of useful hands
Ti! H, Ulrich and A, A, Y. 241, Academic Presgy New
Yorlc+W. It is described in ed. Foerst. "Also, the compound of 2H is, as shown in reaction formula (5),
It can be produced by reacting a sulfonamide of formula (1) with a methyl carbamate of formula (2) in a suitable vortex in the presence of trimethylaluminum. More specifically, a reaction mixture '0 containing a sulfonamide ■ and an inert aprotic solvent such as methylene chloride or toluene is reacted with trimethylaluminum in an inert atmosphere, and the resulting mixture is brought to ambient temperature. , the generation of gas stops, and oyster 1
Zeru. Methyl carbamate■ is generally added in pure form,
The reaction is then allowed to proceed for 16 to 96 hours at ambient to midstream temperatures. The product is aqueous i=(
The product can be isolated by adding ``rj/'' to the reaction mixture and then partitioning the product into methylene chloride. Alternatively, it can be purified by chromatography. In both the methods shown by reaction formulas (4) and (5), R is HXc, -C4 alkyl, S 02 Rlo
%5O2NR,lR1,,CH,N(CH3)2,C
H20CH2CH3 or CH2OCH3 and R2 is C1-C5 alkyl or S 02 c, R
5 is suitable for the preparation of compounds of formula (1). The method of reaction scheme (4) is more preferred for the preparation of compounds 45- in which R2 is H and R has the meaning described above. This method also allows R to be (C
H2) mCO2R9, R9 is other than H, and R2 is H or auto-C3 alkyl. Formula ■ where R is (CR2)mC02R9, R9 is H, and R2 is H or C,-C3 alkyl
are best prepared by alkaline hydrolysis from the corresponding compounds where R9 is cl -C3 alkyl. Compounds of formula (2) in which R is CHO are those in which R is (CR
2) m C02R9, m is 0, and R
It can be prepared from the corresponding compound in which 9 is CH3 (compound 1) by partial reduction using a reducing agent such as diisobutylaluminum hydride. 46 - Procedures for these conversions will be apparent to those skilled in the art. Preparation of reaction products Synthesis of heterocyclic amine derivatives such as the compound of formula ■,
'The Chemstry of fIet
erocyclic Compounds''' Inte
rsscience Publ, published by L-York and London. 2-Aminopyrimidines are described by Futaiwa Nori, J. Brown, ” The Pyrimidines
”, Vol.
, M., Smolin and Tori. Rapoport+ IIs-Triazine a
Vol.
chaeffer), and R, Huffman.
and F,C,5ehaeffer+J,Org,
Chem, 28.1812-1821 (1963
)It is described in. "#, subcyclic amines of formula V in which R5 is CH3 can be prepared by the following procedure, or modifications thereof obvious to those skilled in the art. A solution of amine X in concentrated hydrochloric acid is mixed with an aqueous sodium nitrite solution. react and the chloro compound M is isolated in the conventional manner by filtration of acidic solutions (e.g. Bee and Rose
+ J, Chem, Soc, C,, 2051 (1
966), Z is CH and X and Y are O
CR3). Replacement of chlorine can be accomplished by heating with excess methylamine in water to obtain the methylamino heterocycle. Pyrimidinyl and triazinyl methyl carbamate of formula (1) can be produced by the method shown in reaction formula (6). When the heterocyclic amines k and Rs of formula V are CH3 or H, respectively, they are reacted with 1 equivalent or 2 equivalents of sodium hydride and an excess amount of dimethyl carbamate to produce 1. The reaction is carried out in an inert solvent such as tetrahydrofuran at 25-70°C for 1-24 hours. The product is isolated by (a) addition of 2 equivalents of concentrated hydrochloric acid and aqueous saturated sodium chloride, and (b) separation of the organic phase and subsequent concentration to dryness in vacuo. The production of indole derivatives is carried out in the series"'TheChe
mistry of heteroeyclic
'Indoles' of 'Camp, Ounda'
, Parts 1-4, Vol, XXV and = 49- R, J, Sunderbergw II The Ch
emistry, ofIndoles”XAead
'tIXemic Press (=New York and London) (1970) has been extensively discussed. Two other particularly useful procedures are U.S. Pat. No. 3,901.899 (P, G, Gas+aman) and U.S. Pat. +
, No. 960.92/) (P, G, Gassma
n). Indoles of formula 1, in which R1 is H, c, -c, alkyl or C0tR, and R2 is H or -C3 alkyl, are well known in the literature. R, is H or C, -C, alkyl, and R2
is 5O2C6H5, and R2 is H
From the corresponding compound which is, one equivalent of base, e.g.
-50- prepared by corresponding sodium methylsulfonyl methide or n-butyllithium in ether or tetrahydrofuran and then reacting with phenylsulfonyl chloride (e.g. Sundberg and Ru5selL
-J, Orlg. C, hem, -38, 3324 (1973), and 5aulnier and Gribble, J, Org.
+ Chem. 47.747 (1982)). The indole in 2, where R1 is CORlo, has the reaction formula (
It can be manufactured by method 7). The N-phenylsulfonylindole of formula Upon recooling and quenching with chloride R1, COCl, formula
The compound (1) is produced (see, for example, Saglnier and Gribble, 1btti.). Indole of formula (3), where R1 is 5O2RIO, can be produced as shown in reaction formula (8). Lithiation of Xl1l as described above and subsequent quenching with dialkyl disulfide (RsoS)2 yields N
-phenylsulfonyl-2-alkylthioindole is formed, which is described by Wieland, et. al.
. Justus Liebigs Ann, Che
m, 713.186 (196B) and Hino,
et, al., JaChem. 1. Soc, 5ect, D 473 (1972). An alkylsulfonylindole of formula X■ is produced. Reaction formula (9) represents a method for producing indole of formula (3) in which R1 is So2NR1, R12. Lithiation in this method: X in an inert atmosphere
An ether solution of 1.1 equivalents of LDA was added at 0°C. l) by adding and then stirring for 0.5 to 2 hours at 0°C. Adding the resulting slurry to a solution of 2 equivalents of sulfonyl chloride in an equal volume of hexane at -20°C to -30°C,
After 0.5 to 1 hour at -20 DEG C. to -60 DEG C., the reaction mixture is warmed to ambient temperature, stirred until the reaction is complete (generally 2 to 8 hours), and then diluted with water. N-phenylsulfonyl-2-chlorosulfonylindole lT
, isolated by extraction into acetic acid, and purified by trituration with ether or similar solvent. These products are reacted with excess amine HNR11RI2 according to procedures apparent to those skilled in the art to form indole sulfonamides XVI. R1 is coRlo, 5o2R, 6t or S 02 NR
11'R1□ and R2 is H, the indole of the formula (3), while the corresponding compounds (X+V, XV and
) is produced by alkaline hydrolysis following the procedure of When the product does not precipitate on acidification, it can be isolated by extraction into 1 ft. of ethyl acetate, ether. Alkylation of these indoles or nitrogens by procedures well known in the literature provides R1
is COR16XS 02 RIO or S 02 NR
HRtz and then a compound of formula (1) is obtained in which R2 is CB-C37#kyl. R is H, C17C4furkyl, CH20CHst or =
54- CR20C) T2 CHs f A! l), Soshi R2
is So2c, R5] indole-2-
Sulfonamide is a reaction formula (10) according to reaction formula (9).
It can be manufactured using the following method. (2) The corresponding compound of formula (2) in which L2 is H is prepared by following the procedure of reaction formula (6).
- Can be produced by alkaline hydrolysis. The corresponding compounds in which Nlt2 is auto-C3 alkyl can be prepared by the method shown below. R is HlC, -C4 alkyl, CH, OCH3 or C
The protected indole-2-sulfonamide of formula X■, R20CR2CR3, is prepared by the method of reaction scheme (9). When alkaline hydrolyzed as mentioned above,
XX is obtained, which can be alkylated on the more nucleophilic indole nitrogen after formation of the dianion by procedures known to those skilled in the art. The t-butyl anchor group is then removed with trifluoroacetic acid to yield the desired indole-2-sulfonic acid where R2 is cl-C3 alkyl. Protected indole-2-sulfonamides (compounds XX) of formula Intermediate of compound Indole XX
from -20°C to 0°C in ether or tetrahydrofuran with 2 equivalents of n-butyllithium under an inert atmosphere.
If the reaction is omitted, optionally in the presence of detraethylenediamine, a 6-lithio derivative is obtained. XX Anion of C fc+ e3 alkyl chloroformate, C1-03 alkyl α bromoacetate or c, -
Quenching with C3 dialkyl disulfide and then oxidation in the last case results in each R being (CH2)o CO2R
9, (CIh)ICOzRs or 5O2R1G gives an indole-2-sulfonamide of formula X■. Suitable procedures for these conversions are known. Then, R2 is H or cl-C3alkyl, and R is S02Rso or (CH2)C
Indole-2-sulfonamides of formula 1, in which O2R9 and m is 0 or 1, can be prepared by alkaline hydrolysis of the N-phenylsulfonyl group, where R is (CH2)m
Re-esterify when CO2R, and optionally N
-alkylation and removal of the t-butyl protecting group, the OR that can be prepared is S 02 NRII R
Indole 12 of formula (1) is prepared from the corresponding compound of formula XXI obtained by alkaline hydrolysis of XX according to the procedure shown in reaction formula (12). Xl XX1 Reaction with thionyl chloride to form indole-358--sulfonyl chloride, which is then converted to the sulfo/amide and oxidized to the sulfonamide [Canadian Patent No. 747.920 (J, Szmus
y, kovicz) Director and J, Szmuszko
vicz+J, Org, Cbem, 29.17
9 (1964)]. Optionally alkylating the indole nitrogen followed by hydrolysis of trifluoroacetic acid as described above, lζ
is S Ox NRtt Rts and R2 is H
Alternatively, C1-C, argyl indole ■ can be obtained. Reaction of indole XXIe with acrylic acid in the presence of acetic acid yields indole-3-propionic acid. Esterification, optionally alkylating the indole nitrogen, and carrying out the J-11 moisture of trifluoroacetic acid, ff k, R is (CR2) mC02Rg, m is 2, and R2 is f( -f or C, -C3 alkyl gives an indole of the f-opening formula. After alkylation and complete removal of t-butyl protection, R becomes CR2N
(CR3)2, and R2 is H or cm-C
An indole of the formula ■, which is 3 alkyl, is obtained. Agriculturally suitable JXs of formulas I and 1 are also useful herbicides and can be prepared by several known methods. The compound rules of the present invention and methods of making them are briefly illustrated by the following examples. Unless otherwise specified, all parts are by weight and all temperatures are in °C. Example 1 Methyl 5-([(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]aminesulfonyl]-1-methyl-I H-indole-2-carboxy-7 at 10°C
A stirred suspension of 2.5f (0,021 mol) of 2-amino-4,6-dimethylpyrimidine in dry nitromethane was added by syringe under nitrogen to the 2.0-
(0,023 mol) of chlorosulfonyl isocyanate gold was added in increments of ηgj at a rate such that the temperature was maintained below 0°C. The resulting clear solution total 0,5 hours -5 °C to -10
Stir at a temperature of 40 - 59 °C in dry nitrogen.
When the addition was completed, 2.951 (0,02261-mol) of aluminum chloride (ID' The reaction mixture was stirred at reflux temperature for 6 hours, then cooled to room temperature and poured into 300-mL R20. Methylene chloride was added and the layers were separated. The aqueous solution was poured into two additional portions. Extracted with CR2Cl2 and washed the combined M solution with R20, dried over MgSO4 and evaporated in vacuo. Trituration of the residue with a minimum amount of CH2Cl2 yielded 2
．． The desired product of 021F is a white solid, mp 212-21
Obtained at 5°C (min wl). Absorption of the infrared spectrum of the product: 3215 and 3150 (Nl(), 1730 (C=O
), 1710 (C=O), 1345 and 1150 (
802) tM-”. CH3), 3.88 (B, 6H, ester CHs and N-CR3), 6.90 (s, IH, pyrimidine CH), 7.23-7.75 (m, 3H. Indole nitrogen containing al 6-C47 (m, IH, indole CH), 10.30 (s, I H, NH,)
, 1 & 26 (br s, IH, NH) 062- Mass spectrometry: m/e 123, crystal 3 Example 2 Methyl 3 ([(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]aminesulfonyl] −
Preparation of 1-methyl-I H-indole-2-hydroxylate - 2.92F in 75fnl dry CH3NO2 at 10°C
(0,021 mol) of 2-amino-4-methquin-6-
2.01 nl (0,023 mol) of chlorosulfonyl isocyanate are added dropwise by syringe under nitrogen to the stirred suspension of methylpyrimidine at a rate such that the temperature is maintained below 1°C. Ta. The resulting solution is heated to -5℃~
Stirred for 0.5 h at -10°C, then 3.97 f (0,021 mol) in 25 tnl dry nitromethane.
dropwise contact with a solution of methyl 1-methyl-I H-indole-2-carboxylate. When the addition was complete, 2.95 f (0,022 mol) of aluminum chloride (I) was added all at once. The reaction mixture was strained at reflux temperature for 3 hours, then cooled to room temperature, 300nL
dichloromethane was added and the layers were separated. The water bath was diluted with two [1] portions of CH2Cl.
2, the combined organic solution was washed with N20, and the Mg
Dry with SO4 and evaporate in vacuo. Chromatography on silica gel and elution with 50% acetone in CH2Cl2 gave the desired product, 1.6y, as a white solid, mp 2.
Obtained at 00-203°C (decomposition). Infrared spectrum analysis of the product: 3190 (NH), 1
715 (C=O), 1703 (C=O), 1340 and 1150 (802) crn-' 0 month ■ NMR (CDC13/DMSO-dJδ2.45
(s, SH. Pi+) Mishi:,yCN3), '5.95(s, 3
H,0CH3), 4.0 (s. 6H,OCH3 and N-CH,q), 6.3'
7(s, IH, pyrimidine CH), 7.23-756
(m, 31(, indole CH), al 8-a
47 (m, I H, indole c f(), 9.
50 (s, IH.
A solution of lithium diisopropylamine (prepared from 50 ml of ether and 1.6 moles of n-butyllithium in hexane)
292 g (0,113
A solution of 1-phenylsulfonyl-I H-indole (5 mol) was added dropwise over 40 minutes under nitrogen. The resulting slurry was stirred for 10 minutes at 0°C and then heated by cannula to -20°C to -30°C (dry ice/
1a31d (0,227 mol) in a solution of sulfuryl chloride in a CC14 bath). Near the end of the addition,
There was a gradual fever of 5°C. After further cooling for 30 minutes, the water bath was removed and stirring continued for 4 hours at ambient temperature. Pour the slurry into water and stir in the ethyl acetate.
Added until all solids were dissolved. The layers were separated and the aqueous phase was extracted twice with ethyl acetate. The combined organic solutions were washed with water, dried over MgSO4 and evaporated in vacuo to give a dark semi-solid. Trituration with ether gave 25.072 yellow-brown solids, 41 points 115-118°C. 1, HNMR (CDC13) δ7.17-7.84 (m
, 7H), a03-a21 (m, 2H), 8.36
(d, 11-I, J=9hz, C-3 proton). Infrared spectrum of the product 1385.1180 and 1185 crn-'' (sulfonyl chloride). Example 4 1-Phenylsulfonyl-I I(-(ntho/l/-
Production of 2-sulfonamide 150m7! of 1Or(0,0211
11 mol) of 1-phenylsulfonyl-1H-indo-
In the stirred solution of A/-2-sulfonyl chloride,
At -78°C 4 mJ (0,192 mol) of anhydrous ammonia were added. The resulting slurry was warmed to room temperature for 60 minutes and then sparged with nitrogen to remove excess ammonia. The slurry was poured into a P bath and the P solution was evaporated in vacuo, resulting in a yellowish brown solid of 9.1 SM, melting point 199-200.
．． 5°C was obtained. lH'NMR (CDCI3/DMSO-d6) δ7.2
3-'7.77 (m. 9H), 8.1-8.28 (m, 3H, C-3 proton and 5o2NE (2). Infrared spectrum of product: 3400 and 3280t
M-” (802NH2)0 Example 5 Preparation of 1H-indole-2-sulfo/amide - 2.4 f (7.13 mmol) of sulfonamide 1
Add 5rnI to the solution! 0.86 f(2
1 mmol) of sodium hydroxide solution was added. The resulting mixture'! Refluxed for Q, s hours, then cooled to room temperature, poured into water and slightly acidified with 1N HCI. This solution was extracted twice with total ethyl acetate, and the combined
Drying over gSO4 and evaporation in vacuo gave 0587 a pale yellow-brown solid, mp 190-192°C, 1fI NMR (CDCI3/DMSO-d6) δ6.
92-7.72 (m. 7H), 11.59 (br, IH, Indole NH)
. Infrared spectrum of product: 5385.3280.13
10 and 1140 (So, NH2) and 3340α
-1(indole N1(). Example 6 Preparation of N-((4,6-dimethylpyrimidin-2-yl)aminocarbonyl)-1H-indole-2-sulfonamide 5, O, f (0, 0255 mol) of IH-indole-2-sulfonamide, 2.9d (0.0255 mol) of n-butyl isocyanate, a catalytic amount of 1.4-
Diazabicyclo(2,z,2)octane and 75m1
A compound of xylene was heated to 168° C. under nitrogen. Phosgene was condensed into the reaction mixture as the temperature decreased to 130°C. As the phosgene was consumed, the temperature gradually increased to 138°C. Furthermore, phosgene was added until the reaction temperature could no longer return to 138°C.
I felt stronger. Unreacted phosgene was removed with a stream of nitrogen by flushing with 2N NaOH and heating continued for 15 minutes. The reaction mixture was cooled to room temperature, placed under nitrogen and evaporated in vacuo to give the sulfonylisocyanate intermediate, which was used without further elaboration in the second step of the reaction. 1.5 m in dry acetonitrile. Of (4,4
A solution of the isocyanate (7 mmol) above 0.5 f (4,0
6 mmol) of 2-amino-4,6-dimethylpyrimidine and the mixture was stirred at ambient temperature overnight. The precipitate was collected by -70- filtration and washed with needles (-Y+) to obtain the desired substance.
Mi/carbonyl-1-phenylsulfonyl-1H
-Made of indole-2-sulfonamide]
1 in dilated methylene. 0? (3.0 mmol) of 1-phenylsulfonyl-IH-(n)''-2
- In the slurry of sulfonamide, hiI under gold 7
fj-ilg of a 2 molar solution of trimethylaluminum in toluene at 1. 6 Add 5 ml (3.5 mmol) and mix. The resulting lI color compound is
With Yumuzai, - U Kisunze, then α54? (3 mmol) of methyl (4,6-dimethylbilimisi/-2-yl)
Karbame) k 〃spoken at once. The u compound was stirred under reflux overnight, then cooled to room temperature, poured into 501 nt of 5% HCl in ice water, and stirred for 5 minutes. The layers were separated and the aqueous phase was washed twice with ethyl chloride. The bound M phase was washed with H2O, dried over MgSO4, and evaporated in vacuo to give the desired product. By using the method generally described above and illustrated in Examples 1-7, The compounds listed in the table below can be prepared in a similar manner. 1) Sen i country i country i engineering CJ
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1) Country 1) 1)
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! 1:! ! :Il! 1) 1) 1) 1) Field Preparations Useful preparations of compounds of formulas I and 1 may be prepared by conventional methods. They are powders, granules, tablets, suspensions, emulsions,
Includes hydrating agents, concentrated emulsions, etc. Many of these can be applied directly. The spray preparations can be expanded in a suitable medium and used in spray volumes of a few liters to a few hundred liters/ha. High strength compositions are primarily used as intermediates for further compounding. Broadly speaking, the preparation comprises active ingredients from about 01 to qq*H,'lr, and (a)
and (b) about 1 to 999% of a solid or liquid diluent. More particularly, the preparation will contain these ingredients in approximately the following proportions:
1-10 Oil-based emulsion (including residual emulsion) Aqueous suspension 10-50 40-84 1-2
0 powder 1-25 70-99 0-
5 grains and tablets 195 5-99.9 0-
15 High strength composition 90 qq 0-10 0
-2 US active ingredients and at least 1 surfactant or diluent
Species = 100% by weight. Of course, lower or higher amounts of active ingredient than listed may be present depending on the intended use and physical properties of the compound. A high proportion of superficial active ingredients is particularly desirable and is achieved by incorporation into the product or by mixing in a tank. -100- A typical solid diluent is Watkins
) et al., “Handbook of In5ec
ticideDust Diluents and C
arriersゝゝゝゝゝ, 2nd edition, Dorando Books Co., Ltd.
orland Boolcg, Ca 1 dwe 1
1, N, J, ), but other solids,
Thus natural and synthetic solids may also be used. Adsorbent diluents are also suitable for irrigation agents and concentrated powders. Representative liquid diluents and solvents include Marsden
sden), “5olventB guide”, 2nd edition, Interscience Inc.
. N, Y.), 1950. Solubility below 0.1 is suitable for concentrated suspensions; concentrated solutions are preferably stable to phase separation at 0°C. “McCutcheon's Detergents
andEmulsifiers Annual”
, Allured Publ.
orp, , N, J, ), and Sisely
and Wood, “Encyclop.
erlia of 5 surface Activ
eAgents'', Chemical Publishing Co., Ltd.
Publ, Go, Inc, , N, Y, ), 1
964 indicates surface activity and its recommended uses. All preparations may contain small amounts of additives to reduce foaming, caking, corrosion, microbial growth, etc. Methods for producing such compositions are well known. Solutions are prepared by simply mixing the components. Fine 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, US Pat. No. 5.0).
No. 60.084]. Granules and tablets may be produced by spraying the active substance onto preformed granular carriers or by agglomeration methods. References, J. E. Browning (Bro
Wning), “AgglG-merationゝ1
,Chemical Engineering. December 4 issue, p. 147 (1967), and Berry (p.
erry), Chemical Engineer
'5 Handbook, 4th edition, pages 8-59, McGraw-Hill, N.Y.
1963. For further literature on preparative techniques see, for example: H, M, A-Loux, U.S. Pat. No. 3.23.
5°361, column 6, line 16 to column 7, line 19 and Examples 10 to 41°R, W, Luckenbaugh, U.S. Pat. No. 3.309.192, column 5, lines 43 to 7. Column line 62 and Example 8.12.15.39.41.52.
53.58.132.138~140°162~164
．． 166.167.169~182゜■, Gy
ain) and E. Knusli, 103- U.S. Patent No. 2.891.855, lines 166-5
(Line 4117 and 7°C Examples 1-4°G, C. Klingman, “W
eedContral as a 5cienc
e'ゝ, John Wiley & Sons, Inc.
n WiIey and Sons, Inc.
, Y, ), 1961, IN-96Q. J. D. Fryer and S./L. Evans, “Weed Contro.
l Handbook'', 5th edition, Blackwell Scientific Publications (Rla
cckwellScientificPublicat
ions, C)xford), 1968, 101-1
Page 03. In the following examples, all parts are by weight unless otherwise indicated. Example 8 Wettable powder 104-3-[((4-methoxy-6-methylbiester)
80% sodium alkylnaphthalene sulfonate
2% Sodium ligninsulfonate 2% synthetic amorphous silica 3% Kaolinite
Thirteen pieces of the above ingredients were mixed and ground in a hammer mill to an average particle size of 50 microns or less. This material was remixed and packaged. Example 9 Irrigation agent aminosulfonyl co-1-methyl-1H-indole-2-carboxylic acid, methyl ester
50% sodium alkylnaphthalene sulfonate 2% low viscosity 1 (methyl cellulose)
2 Chikeisou soil
Section 46: Blend the above ingredients, coarsely hammer mill,
Air milling then produced particles that were essentially all 10 microns or less in diameter. After the product was reformulated, it was packaged. Example 10 Granule Wettable powder of Example 9 5 Thiatapulgite particles (US standard sieve No. 20-40;
84-042 I) A slurry of water-friendly powder containing 25% 95% solids was sprayed onto the surface of the attapulgite particles in a double cone mixer. The particles were dried and packaged. Example 11 Extruded tablet 3-[(46-Simethoxy 1,3.-5-thyl ester 25% anhydrous sodium sulfate 10% crude calcium sulfonate 5% sodium alkylnaphthalene sulfonate 1 dicalcium/magnesium bentonite 59% above The ingredients were mixed, hammer milled, and then moistened with approximately 12% water. The mixture was extruded as cylinders approximately 6 mm in diameter, which were cut into tablets 3 mm in length. The tablets could be used directly after drying or the dried tablets could be crushed and subjected to US Standard Sieve No. 20 (opening o, a 4, ). US Standard Sieve No. 40 (opening 0, 42 am). ) was packaged for use and the bottom of the sieve was circulated. Example 12 107 - Oily Suspension Dhol-2-Carboxylic Acid, Methyl Ester
25 polyoxyethylene sorbitol hexaoleate
5 t higher aliphatic hydrocarbon oil 70 t The above ingredients were ground together in a sand mill to reduce solid particles to less than about 5 microns. The resulting suspension was applied directly, preferably after being extended with oil or emulsified in water. Example 13 Wettable powder chill-1H-indole-2-sulfonamide
2o% Sodium alkylnaphthalene sulfonate 4 Sodium tiliigenin sulfonate
4th 108- Low viscosity methylcellulose 3thiatapalgite 69th The above components were well blended. After milling in a hammer mill to produce particles substantially all below 100 microns, the material is reformulated and passed through a No. 50 U.S. standard sieve (0.3 aperture).
) and packaged. Example 14 Low strength granules sulfonamide 1 tN, N
- Dimethylformamide 9 Thiatapulgiaite particles 90 mesh (US standard sieve 20-40 mesh) The active ingredient was dissolved in a solvent and the solution was sprayed onto the dedusted particles in a double cone mixer. After spraying the solution was completed, the mixer was activated briefly and the particles were then packaged. Example 15 Aqueous suspension medium
4 o% polyacrylic acid thickener 0.3 Dodecyl phenol polyethylene glycol ether
0.5% disodium phosphate
Sodium monotyphosphate 0.
5 parts polyvinyl alcohol 1.0 parts water
The ingredients listed in Tables 56 and 7 were blended and ground together in a sand mill to produce particles essentially all below 5 microns in size. Example 16 Solution N-, ((+-methyl-6-medoxy 1° water
95%
Add the above salt directly to water while stirring to form a solution;
This can then be packaged for use. Example 17 Low Viscosity Granules Sulfonamide 0.1% The above properties were dissolved in a solvent and the solution was sprayed onto the dedusted particles in a double cone mixer. After spraying the solution was complete, the material was warmed to evaporate the solvent. The material was cooled and then packaged. 111 - Example 18 Granule Wetting Agent 1 Thiatabulgite clay 9% - The above ingredients were blended, milled and passed through a 100 mesh sieve. The material was then added to a fluidized bed granulator, the airflow was adjusted to gently fluidize the material, and a fine mist of water was sprayed onto the fluidized material. Flowing and atomizing continued until particles in the desired size range were produced. Spraying was stopped, but fluidization was continued with heating as required to reduce the moisture to the desired level, generally less than 1%. This material is then drained and sieved to the desired range, typically 14 to 100 mesh (1410-1
49 microns) and packaged for use. Example 19 High Thickener 1-2-Carboxylic Acid, Methyl Ester 99% Silica Airgel 05% Synthetic Amorphous Fine Silica 05% The above ingredients were mixed and ground in a hammer mill to ensure that essentially all U.S. A highly thickened agent was produced that passed through a standard sieve No. 50 (between openings 03). This substance can be further used in the production of preparations if desired. Example 20 Irrigation agent 1-2-carboxylate: Methyl ester 90% Sodium dioctyl sulfosuccinate 01% Synthetic fine silica 9.9% The above hX components were blended in a hammer mill and pulverized, and all Particles were produced in which the particle size was less than 100 microns. The material was sieved through a No. 50 US standard sieve and then packaged. Example 21 Water Conservancy Acid, Methyl Ester 40 Sodium Tiligenin Sulfonate 20 Thymontomorillonite Clay 40 The above ingredients were well blended, roughly hammer milled and then air milled until essentially all of them were below 10 microns. Particles of size were produced. This material was reformulated and then packaged. Example 22 Oil suspension sulfonamide 35% polyalcohol carbonated Nystert blend with oil-soluble petroleum sulfonate 6% xylene
Section 59 The above ingredients were combined and ground together in a sand mill to produce particles that were essentially all 5 microns or less. The product can be used directly, extended with oil, or emulsified in water. Uses The compounds of the invention are potent herbicides. Those-115
- pre-emergence of weeds in areas where complete eradication of all vegetation is expected, such as riversides of fuel storage tanks, around ammunition depots, industrial storage areas, parking lots, amphitheaters, around billboards, highways and railway areas; and/or exhibit broad utility for post-emergence control. Alternatively, the compounds are useful for selectively controlling weeds in crops such as wheat, cotton, and soybean. The rate of use of the compounds of the invention will depend on their use as selective or systemic herbicides, the coexisting crop species, the weed beds to be controlled, the weather and climate, the formulation chosen, the method of application, the amount of foliage present, etc. Determined by many factors including: Generally speaking, the compounds should be used in amounts of about 0.03 to 10 K9/ha. In this case, low doses in the ranges mentioned above may be used when used on light soils and/or soils with low organic matter content, when selectively controlling weeds, or when only short-term persistence is required. is used. The compounds of the invention can also be used in combination with other commercially available herbicides, such as those of the triazine, triazole, uracil, urea, amide, diphenyl ether, carbamate and bipyridylium types. The activity of these compounds was discovered in greenhouse tests. The test method and results are as follows. Test A Kingfisher (Digitaria 8p, ), Golden millet (Echinochloa crusgalli),
Oat (Avenafatua), Ebisugusa (C
assiIILtora), morning glory (Ipomoea
l1ip, ), Onamomi (X a -ntium
Seeds of sorghum, maize, soybeans, rice, wheat, and tubers of sedge are planted in a growth medium and treated before germination with a compound of Table A dissolved in a solvent that is harmless to the plants. I did this. At the same time, cotton with three leaves (including cotyledons), kidney bean with the sixth three leaflets spreading, crabgrass with two leaves, goldenberry with two leaves, oat with two leaves, oat with three leaves Shrimp grass with leaves (including cotyledons), morning glory with four leaves (including cotyledons), Japanese sorghum with four leaves (including cotyledons), four-leaf sorghum, four-row corn, dice with two cotyledons, trifoliate Rice, -leaf wheat, and 6 to 5-leaf trifolium were sprayed with a solution of the compound in a solvent that is non-toxic to the plants. Treated plants and control 41σ plants were kept in the greenhouse for 16 days and all stems were compared to the control and the response to treatment was visually assessed. Evaluation of compounds tested by this procedure is listed in Table A. As is evident from this table, the tested compounds have high herbicidal activity, and the compounds suppress weeds in wheat and soybean. The evaluation method used was based on the shaku4 scale from 0 (no effect) to 10 (maximum effect) of 1. The accompanying letter symbols have the following meanings. G-growth retardation; C-bleaching/necrosis; 6Y abscission of single buds or flowers; U-abnormal color formation; E-inhibition of germination; H-effects of formation; P=terminal bud damage- 119-499 Test B Two plastic bulb pans were filled with fertilized and limed Fallsington silt loam soil. One pan contains corn, sorghum, and Kentucky bluegrass.
ntucky blueglaas) and various herbaceous plants. Other pans were planted with cotton, soybeans, Cyperus rotundus, and various broadleaf weeds. The following herbaceous plants and broad-leaved weeds were planted. Japanese crabgrass (Digitalia sangui)
nalis), Golden millet (Ech i nochloa)
crusgalli), oat (Avena f.
atua), Johnson grass (Sorghum h.
alepense), dallis grass (Pagpalum)
dilatatum), Seta
ria faberii), Br.
omus 5ecalinus), mustard (Bra
ssica arvensis), Onamomi 125- 124- (Xantium pennsylvanicum)
, Amaranthus retrofl
exus), morning glory (Ipomoea heder)
acea), Episgusa (Cassia tora)
, teaweed (Sidaspinosa), velvet leaf (Abutilontheophrasti)
), and Datura (1) atura s.
tramonium). Furthermore, 2 with a diameter of 12.5cn1
Rice and wheat were planted in two pots filled with prepared soil. I planted sugar beet in the other 12.5z pot. The above four containers were pre-emergent treated with several test compounds falling within the scope of the invention. After 28 days of treatment, the response of the plants to the chemical treatment was visually evaluated using the evaluation system described above in Test A. This data is shown in Table 8. Certain compounds are found to be useful in controlling weeds in crops such as soybean, wheat and cotton. 126-

Claims (1)

[Claims] 1. In the formula, R is H% CI C4 alkyl, (CHz ) mC0
2R9, CH2CO21-15, 5o2R1o, CH
O1So2NRIIR12, CHz N (CR3)
t or CHz OCR3, R1 is I(,C,
-C4 alkyl, CO2R6, C(0)NRyRsXC
(0) RtoXSO2RtoX or S 02 N
RI lR12; R2 is H, c, -c3 alkyl or 5O2C6■■51-; R3 is H, F', CI, Br, Cl-03 alkyl, C, -C3 alkoxy sweet or No, Yes; R4 is H
, CI-4 or Br; R5 is H-f or CH
3; R6 is c, -C, alkyl, C3-c, alkenyl, C
or CH2CH20CH3; R7 and R8 are independently H or C, -c. alkyl, with the total number of carbon atoms being less than or equal to 4; R9 is H or C1 -C
5 alkyl; RIO is a, -C3 alkyl; R11 and R12 are independently c, -C3 alkyl, with the total number of carbon atoms being less than or equal to 4; m is 0.1 or 2; = 2- X is C1 (3'E or OCH3; Y is Cll3,
OC■(3,0C2II5,CH20C)R3,CI,
FT, C2kls or N(CH3)2; 2 is CH or N, provided that when R2 is 5O2C6H5, RI and R are H or CI-C3 alkyl, 2) Y is When CI, 2 is CH; and 3) When m is 0, R9 is C,-C3 alkyl. Z In the above formula I, R, is H, ct-c3 alkyl, CO2R6, C(0)NR? Rs, So, NR11R
12 or SO2'R1o; and R5 is H. 3. The compound according to claim 2, wherein R3 and R4 are H. 4. R2 is 8 dimensions or CH3, claim 3
Compounds described in Section. 5, R1 is HXCO2CH3, SO□CH3 or 5O
5. The compound of claim 4 which is 2N(CH3)2. 6, Y is CR3, OCR3, OC2R5, CI(2
6. A compound according to claim 5, which is 0CH3 or CI. 2 In the above formula (■), R is HXcl-c, alkyl,
(CHz) mCO2Rg, 5OzRto or 802
2. A compound according to claim 1, wherein NRlt R12; and R5 is H. & R3 and R4 are H, claim 7
Compounds described in Section. 9. The compound according to claim 8, wherein R2 is H or (JI3). 10, R is HXCH3-! or (CH2)mCO2-(
C1-03 alkyl). 11, Y is CH3,0CR3,QC,H,,CHz O
CHs'! or C1. 12, 5-[:((4,6-Simethoxypyrimidin-2-yl)aminocarbonylcoaminosulfonyl]-1
-Methyl-1H-indole-2-carboxylic acid, methyl ester, the compound according to claim 1. 13, 3-[((4,6-dimethylpyrimidine-2-
2. The compound according to claim 1, which is methyl)aminocarbonylcoaminosulfonyl-1-methyl-1H-indole-2-carboxylic 5-acid, methyl ester. 14, 3-[[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonylcoaminosulfonyl]
The compound according to claim 1, which is -1-methyl-1H-indole-2-carboxylic acid, methyl ester. 15, 3-([(4,6-Simethoxy1.3.5-
The compound according to claim 1, which is triazin-2-yl)aminocarbonylcoaminosulfonyl]-1-methyl-1H-indole-2-carboxylic acid, methyl ester. 16, 3-(((4,6-simethoxy1.5.5-
) riazin-2-yl)aminocarbonyl]aminesulfonyl]-1-methyl-1H-indole-2-carboxylic acid, methyl ester. 6- 17 3-[(4-methyl-6-medoxy 1.3.5
=triazin-2-yl)aminocarbonylcoaminosulfonyl]-1-methyl-I H-indole-2-carboxylic acid, methyl ester, Claim 1
Compounds described in Section. 1a, N-((46-cymethoxypyrimidin-2-yl)aminocarbonyl]-3-mef-I H-indole-2-sulfonamide, Claim 1
Compounds described in Section. 19, the compound according to claim 1, which is N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-3-methyl-1E(-indole-2-sulfonamide. 20 , N-((4-methyl-6-medoxypyrimidin-2-yl)aminocarboxyl]-3-methyl-1H-indole-2-sulfonamide, the compound according to claim 1 2j, N-((4,6-Simethoxy1.3.
s-triazin-2-yl)aminocarbonyl]-3
-Methyl-I H-indole-2-sulfonamide. 22, N-[(4,/l-dimethoxy-1,3,5
-triazin-2-yl)aminocarbonyl-6-methyl-111-indole-2-sulfonamide. 25N-((4-methyl-6-medoxy1.3.5
-triazin-2-yl)aminocarbonyl]-3-methyl-1H-indole-2-sulfonamide,
A compound according to claim 1. 24, 3-[((4,6-cymethoxypyrimidine-2
-yl)aminocarbonyl]aminesulfonyl]-I
The compound according to claim 1, which is H-indole-2-carboxylic acid, ethyl ester. 25, x-[((46-Simethoxy1.5.5-t9aziee-2-yl)aminocarbonyl]aminosulfonyl)-1H-indole-2-carboxylic acid, ethyl ester, Claim 1 Compounds described in Section. 26, 3-(((4-methoxy-6-methyl-1',
3.5-triazin-2-yl)aminocarbonylcoaminosulfonyl':l-11-I-indole-2
- The compound according to claim 1, which is a carboxylic acid, ethyl ester. 27, 3-[[(4-methoxy-6-methylpyrimidiy-2-yl)aminocarbonylcoaminosulfonyl]
-1H-indole-2-carbo/acid, ethyl ester, the compound according to claim 1(n). 2a s-([(4,6-dimethylpyrimidine-2-
The compound according to claim 1, which is 9-l)aminocarbonylcoaminosulfonyl]-1H-indole-2-carboxylic acid, ethyl ester. 2. It is characterized by containing an effective amount of the compound according to claim 1 and at least one of a surfactant, a solid or liquid inert diluent, A composition for suppressing the growth of undesirable plants. 30, an effective amount of the compound according to claim 2,
1. A composition for inhibiting the growth of undesirable plants, comprising a surfactant and at least one solid or liquid inert diluent. 31, an effective amount of the compound according to claim 3,
7. A composition for inhibiting the growth of unyielding plants, characterized in that it contains a surfactant (3) and at least one glaze of a solid or liquid inert diluent. 32, an effective amount of the compound according to claim 4,
1. A composition for inhibiting the growth of desirable plants, comprising a surfactant and at least one solid or liquid inert diluent. 33, an effective amount of the compound according to claim 5,
Composition 1 for suppressing undesirable plant growth, characterized in that it contains a surfactant and at least one solid or liquid inert diluent.
1 Of course. 34, an effective amount of the compound according to claim 6,
1. A composition for inhibiting undesirable plant growth, comprising a surfactant and at least one solid or liquid inert diluent. 35, an effective amount of the compound according to claim 7,
1. A composition for inhibiting undesirable plant growth, characterized in that it contains a surfactant and at least one solid or liquid inert diluent. 36, an effective amount of the compound according to claim 8, and at least 1a4 of a surfactant and a solid or liquid inert diluent,
A composition for inhibiting undesirable plant growth. 37, an effective amount of the compound according to claim 9,
A glaze for inhibiting undesirable plant growth, comprising a surfactant and at least one glaze of a solid or liquid inert diluent. 6a% effective amount of the compound according to claim 10;
1. A composition for inhibiting undesirable plant growth, comprising a surfactant and at least one solid or liquid inert diluent. 7, characterized in that it contains 39% of the effectiveness of the compound according to claim 11, and at least one surfactant and a solid or liquid inert diluent.
A composition for suppressing the growth of plants that do not grow. 40. A method for suppressing the growth of undesirable plants, which comprises applying an effective amount of the compound according to claim 1 to the area to be protected. 41. 7. A method for completely suppressing the dead heads of plants that are not fragile, characterized by applying an effective amount of the compound described in claim 2 to the area to be protected. 42. A method for suppressing the growth of plants that do not grow in size 7 to 13-4, characterized in that an effective amount of the compound according to claim 3 is applied to the area to be protected. A method for inhibiting undesirable plant growth, which comprises applying an effective amount of the compound according to item 4 to a site to be protected. 44. A method for suppressing undesirable plant growth, which comprises applying an effective amount of the compound according to claim 5 to the area to be protected. 45. A method for suppressing the growth of undesirable plants, characterized by applying an effective amount of the compound according to claim 6 to the area to be protected. 046: The compound according to claim 7 7. A method for suppressing the growth of plants that do not grow in size, the method comprising applying an effective amount of the same to a place to be protected. 04aClaim 9
14- A method for inhibiting undesirable plant growth, characterized in that an effective amount of a compound according to paragraph 1 is applied to the area to be protected. 42. A method for suppressing the growth of undesirable plants, which comprises applying an effective amount of the compound according to claim 10 to the desired area. 50. A method for inhibiting undesirable plant growth, which comprises applying an effective amount of the compound according to claim 11 to a site to be protected.