JPH01139582A - Production of sulfonylurea derivative - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (Q is condensed heterocyclic ring having N atom in the bridgehead which may have a substituent group; R1 and R2 are alkyl, alkoxy or halogen; Z is CH or N). EXAMPLE:N-(2-Chloroimidazo[1,2-a]pyrimidin-3-ylsulfonyl)-N'-(4,6-dimet hoxy-2- pyrimidinyl)urea. USE:A herbicide. PREPARATION:A compound expressed by the formula Q-SO2NH2 is reacted with a compound expressed by formula II [Y1 is halogen or -OY2 (Y2 is alkyl or phenyl)] in the presence of a base. The resultant reaction mixture is then reacted with a compound expressed by formula III together with an acid under anhydrous conditions.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a novel sulfonylurea derivative having herbicidal activity.

The sulfonylurea derivatives obtained by the method of the present invention (described in Japanese Patent Application No. 62-56250) are novel and useful as agricultural chemicals such as herbicides.

(Prior art and problems to be solved by the invention) Up until now, the method for producing sulfonylurea derivatives has been to react a pyrazole or phenylsulfonamide compound with a chloroformic acid ester or a carbonic acid diester to produce a sulfonyl carbamate compound. A two-step method is known in which the compound is isolated and purified and then reacted with an amine compound. For example, in Japanese Patent Application Laid-Open No. 60-78980, the formula [
In the formula, A is hydrogen, lower alkyl; A is hydrogen, lower alkyl; D is hydrogen, lower alkyl, -COOR, (R is hydrogen, lower alkyl); E is alkyl, phenyl; G is nitrogen, =♀ -r ('(R' is hydrogen): M and M' each independently represent hydrogen, lower alkyl, lower alkoxy, etc.) A two-step production method is described.

However, this method (1) requires two steps and is complicated to operate (
2) The yield of the final target compound is low and high purity cannot be obtained. (3) The sulfonyl carbamate compound as an intermediate compound has disadvantages such as being unstable to moisture and heat and difficult to handle. This cannot necessarily be said to be satisfactory.

(Means for Solving the Problems) The present invention is based on the general formula %() [wherein Q represents a fused heterocyclic group having an N atom at the bridge head which may have a substituent] Compounds with the general formula [wherein Y is a halogen atom or -OY, Y.

represents an alkyl group or a phenyl group] in the presence of a base, and then the reaction mixture is added under anhydrous conditions to a compound represented by the general formula [wherein R1 and R1 are an alkyl group, an alkoxy group, or a phenyl group, respectively] A compound represented by the general formula [the symbols in the formula have the same meanings as above] is characterized in that a compound represented by a halogen atom, Z represents CI-1 or N] is reacted with an acid. Regarding the manufacturing method.

That is, the present invention provides U.
Without isolating the sulfonyl carbamate compound represented by the general formula % formula % ( ) [the symbols in the formula have the same meanings as above] from the reaction mixture, this sulfonyl carbamate compound was then converted to the general formula ( The present invention provides a method for producing compound (I) more easily, with higher purity, and in higher yield by reacting with the compound represented by n).

All of the compounds (1) produced by the present invention are new compounds that have not been described in any literature.

In the above general formula, Q represents a fused heterocyclic group having an N atom at the bridge head which may have a substituent, and here the fused heterocyclic group having an N atom at the bridge head refers to the tip of the bridge bond. It means a fused heterocyclic group in which both or one of the terminal atoms, ie, the bridgehead atoms, are nitrogen atoms. The fused heterocyclic group having an N atom at the bridgehead which may have a substituent represented by Q is, for example, a compound represented by the general formula [wherein, ring This refers to a group formed by leaving one hydrogen atom bonded to a constituent carbon atom other than the bridgehead from the fused heterocycle represented by . Such a fused heterocyclic group is represented by, for example, the general formula [wherein - represents a bond, and the other symbols have the same meaning as a surface].

A nitrogen-containing heterocycle represented by ring Ⅰ or ring contains 1 to 4 g of nitrogen atoms, and further contains 1 to 3 oxygen atoms or/and 1 to 3 sulfur atoms (even if mono- or dioxidized). 4- to 8-membered, preferably 5- or 6-membered heterocycle which may contain
Furthermore, 5- or 6-membered alicyclic rings (e.g., cyclopentane, cyclohexane), aromatic rings (e.g., benzene, naphthalene),
It may be fused with a heterocycle (preferably a 5- to 6-membered heterocycle).

Among these, general formula A group represented by is preferred.

In the above formula, ring (■) preferably represents a 5-membered heterocycle having 1 to 3 nitrogen atoms, and ring (2) is preferably l or,
It denotes a 6-membered hinocycle with 2 nitrogen atoms or a 5-membered heterocycle containing 1 or 2u nitrogen atoms and 1 sulfur atom (which may be mono- or dioxidized).

Ring (■) and ring (■) each have a substituent B defined later 1.
1 to 3 of B t and B s may be substituted the same or differently.

Specifically, the group represented by the general formula is, for example, the general formula -Fukudai [In the above formula, A is a group forming a condensed ring at the [1,2] position of the imidazole ring, and A' is a group forming a condensed ring at the [1,2] position of the imidazole ring. of [1,
5], A'' is a group forming a fused ring at the [1,5] position of the pyrazole ring, and A″' is a group fused at the [1,2] position of the pyrrole ring. The group forming the ring is Δ
"" represents a group forming a condensed ring at the [3°4] position of the triazole ring, and B1. B- and B3 are each a hydrogen atom, a hydroxy group, an amino group, a cyano group, a sulfamoyl group, and a sulfamoyloxy group.

mercapto group, nitro group, halogen atom or organic residue]. Groups A, A', A''.

The carbon and nitrogen atoms of the ring atoms of A / / / and A / / / / can be substituted with appropriate substituents, such as a hydroxyl group, an amino group, a cyano group, a sulfamoyl group, a sulfamoyloxy group, a mercapto group, a nitro group, halogen atom.

1 to 3 of the same or different substitutions may be made with organic residues or sulfo groups, and further, adjacent carbon atoms and nitrogen atoms, and carbon atoms and carbon atoms may be substituted with another condensed ring (5 to 3 carbon atoms).
A 6-membered condensed ring) may be formed, and the sulfur atom of the ring-constituting atom may be mono- or diokindized.

The organic residue represented by B + , B t or B is
It has the same meaning as the organic residue of the substituent on the fused heterocycle defined later.

The group A, A', A", A"' or A / / / / contains 1 to 4, preferably 3 to 4, carbon atoms as ring atoms, and further contains 1 to 3 nitrogen atoms, It may contain an oxygen atom and/or a sulfur atom (which may be mono- or no-oxidized).

general formula General formula that is the skeleton of the group represented by (Hereafter, extra white) general formula General formula that is the skeleton of the group represented by -Cost of clothes General formula that is the skeleton of the group represented by general formula General formula that is the skeleton of the group represented by general formula General formula that is the skeleton of the group represented by Can you give me something like that?

Among the above condensed rings, (hereinafter referred to as blank) 2,3-dihydroimidazo[2,1-b]thiazole (
1,2,4)) Liazolo[3,4-b]thiazole Particularly preferred are imidazo[1,2-a]pyridine, imidazo[2,1-b]thiazole, imidazo[1°2-b
] Pyridazine. Most preferably imidazo[1,2
-a] pyrinone.

As mentioned above, the fused heterocyclic group having an N atom at the bridgehead represented by Q is a group formed by removing one hydrogen atom bonded to a constituent carbon atom other than the bridgehead atom of the heterocycle,
For example, the fused heterocyclic group corresponding to imidazo[1;2-a]pyrinone, which is a fused heterocycle, is preferably a group represented by the formula %.

Group A preferably has 4 carbon atoms as ring atoms,
2 to 3 carbon atoms and 1 nitrogen atom, 2 carbon atoms and 1 sulfur atom (which may be mono- or dioxidized), 1 carbon atom, 1 sulfur atom and 1 nitrogen atoms, or one carbon atom and two nitrogen atoms.

The groups A' and A''' preferably contain 4 as ring atoms.
Contains carbon atoms.

The group A // preferably contains as ring atoms 4 carbon atoms, 3 carbon atoms and 1 nitrogen atom, 2 carbon atoms and 1 sulfur atom.

J, %A//// preferably contains 2 carbon atoms and 1 sulfur atom.

The fused heterocyclic group having an N atom at the bridgehead is, for example, a hydroxo group, an amino group, a cyano group, a sulfamoyl group, a sulfamoyloxy group, a mercapto group, a nitro group, a substituent such as a halogen atom 7 organic residue or a sulfo group. 1 to 3 may be substituted the same or differently.

Among the above, preferably a cyano group, a sulfamoyl group,
A sulfamoyloxy group, a nitro group, a halogen atom, or an organic residue. Particularly preferred are a cyano group, a halogen atom, and an organic residue.

Here, the halogen atom means, for example, fluorine, chlorine, bromine, iodine, etc. Organic residues include, for example, hydrocarbon groups, heterocyclic groups, anlu groups, 2-T-QO [in the formula,
Q represents a hydrocarbon group, a heterocyclic group (0)n or an acyl group, and T represents 0. S or S-8, n
represents 0.1 or 2].

a base group or an acyl group, Q represents a hydrocarbon group or an acyl group] A group represented by the formula 1, a carbamoyl group, a carbamoyloxy group, a ureido group, a thiocarbamoyl group, a carboxyl group Or it means a group represented by the formula -OSot Qt [wherein Q has the same meaning as defined above].

Examples of the above organic residues include hydrocarbon groups, heterocyclic groups, acyl groups, hydrocarbon groups, heterocyclic groups, acyl groups represented by Q, and hydrocarbon groups and acyl groups represented by Ql or Q. This is explained in detail below.

The above carbamoyl group and carbamoyloxy group.

The ureido group or thiocarbamoyl group may be substituted with one or two of the same or different hydrocarbon groups, polycyclic groups or acyl groups as detailed below.

Heterocyclic group and Q as examples of organic residues. The heterocyclic group in is a hydrocarbon group explained in detail below.

Acyl group, may be substituted with not 1 (53) halogen atoms.

Here, the hydrocarbon group is an aliphatic group that may have a linear, monobranched or cyclic double bond or triple bond, or an aryl group, an aralkyl group, specifically an alkyl group,
Alkenyl group, alkynyl group.

It means an aryl group or an aralkyl group, and the alkyl group preferably represents a linear monobranched or cyclic alkyl group having 1 to 6 carbon atoms, such as methyl.

Ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 5eC-butyl, tert-butyl, n-
Pentyl, 5ec-pentyl, isopendel, neopentyl.

Cyclopendel, n-hexyl, isohexyl, cyclohexyl, etc. are used, and the alkenyl group preferably represents a linear monobranched or cyclic alkenyl group having 3 to 6 carbon atoms, such as allyl, isopropenyl, l- Butenyl, 2-pentenyl, 2-hexenyl, etc. are used, and the alkynyl group preferably represents an alkynyl group having 3 to 6 carbon atoms, such as propargyl, 2-butynyl, 3-butynyl, 3-pentynyl, 3-hexenyl, etc. The aryl group is preferably an aryl group having 6 to 14 carbon atoms, such as phenyl, naphthyl, biphenylyl, anthryl, etc., and the aralkyl group is preferably an aralkyl group having 7 to 19 carbon atoms. For example, benzyl, phenethyl, phenylpropyl, biphenylylmethyl, benzhydryl, trityl, etc. are used, and the heterocyclic group includes, for example, a nitrogen atom (which may be oxinated), an oxygen atom, a sulfur atom (mono- or dioxidized), 5- to 6-membered heteroatoms containing 1 to 4 heteroatoms such as
~6-membered heterocyclic group and may contain 1 to 4 heteroatoms such as nitrogen atoms (which may be oquinodized), oxygen atoms, and sulfur atoms (which may be mono- or dioxidized) Indicates a fused ring group with a 5- to 6-membered ring, specifically 2- or 3-pyrrolyl.

3-14- or 5-pyrazolyl, 2-. 4- or 5
-imidazolyl, 1,2.3-triazol-4-yl, I, 2.1-)lyazol-3-yl, 11-[- or 211-tetrazol-5-yl, 2- or 3-
furyl, 2- or 3-thienyl, 2- or 3-thienyl-1,1-dioxide, 2-14- or 5-oxasilyl, 3-. 4- or 5-isoxazolyl, 1,
2.3-oxadiazole=4- or 5-yl, I,
2.4-year-old xadiazol-3- or 5-yl, 1,
2.5-oxadiazol-3- or -4-yl, I
, 3.4-oxadiazol-2- or 5-yl, 2
−． 4- or 5-thiazolyl, 3-. 4- or 5-
Isodeazolyl, 1,2.3-thiadiazol-4- or 5-yl, 1,2.4-thiadiazol-3- or 5-yl, I, 2,5-thiadiazol-3- or 4
-yl, 1.3.4-thiadiazole-2- or -5
-yl, 2- or 3-pyrrolinonyl, 2-. 3- or 4-pyridyl, 2-. 3- or 4-pyridyl-N-
oxide, 3- or 4-pyridazinyl, 3- or 4
-pyridazinyl-N-oxide, 2-. 4- or 5-
Pyrimidinyl.

2-14- or 5-pyrimidinyl-N-oxide, pyrazinyl, 2-. 3- or 4-piperidinyl, piperazinyl, 3H-indol-2- or 3-yl, 2-
．． 3- or 4-pyranyl, 2-. 3- or 4-thiopyranyl, 2-', 3- or 4-thiopyranyl-1,
1-dioxide, benzopyranyl, 3-, /l-,5
-,6-,7- or 8-quinolyl, pyrido[2,3-
d] pyrimidinyl (e.g. pyrido[2<3-d]pyriminon-2-yl), I, 5-. 1.6-.

1.7-, 1.8-. 2,6- or 2,7-naphthyridine (e.g. 1,5-naphthyridine-2- or 3-
), Cheno[2,3-d]pyridyl (e.g., Cheno[
2,3-d]pyridin-3-yl), pyrazinoquinolyl (e.g. pyrazino[2,3-d]quinolin-2-yl),
Chromenyl (e.g., 2H-chromen-2- or 3-yl) is used, and the acyl group represents an acyl group derived from an organic carboxylic acid, such as an alkanoyl group, preferably an alkanoyl group having 1 to 7 carbon atoms. groups (e.g., formyl, acedel, propionyl, butyryl, isobutyryl, pentanoyl, hexanoyl, heptanoyl, etc.), arylcarbonyl groups, preferably aryl-carbonyl groups having 6 to 14 carbon atoms (e.g., benzoyl, naphthalenecarbonyl, etc.), alkoxycarbonyl group, preferably an alkoxy-carbonyl group having 1 to 6 carbon atoms (e.g., methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, 5ec-butoxycarbonyl, tert-butoxycarbonyl, etc.), aryl Oxycarbonyl group, preferably an aryloxy-carbonyl group having 6 to 14 carbon atoms (e.g. phenoxycarbonyl group), an aralkylcarbonyl group, preferably an aralkyl-carbonyl group having 7 to 19 carbon atoms (sequence, benzylcarbonyl, phenethylcarbonyl, Phenylpropylcarbonyl.

benzhydrylcarbonyl, naphthylethylcarbonyl, etc.), 5- to 6-membered heterocyclic carbonyl groups (e.g., 2-13- or 4-pyrrolylcarbonyl, 3-.4- or 5-pyrazolylcarbonyl, 2-.4- or 5-imidazolylcarbonyl, 1,2.3-triazol-4-ylcarbonyl, 1,2,4-triazol-3-ylcarbonyl, IH- or 2H-tetrazol-5-ylcarbonyl, 2- or 3-furyl Carbonyl, 2- or 3-thienylcarbonyl, 2-.4- or 5-oxasilylcarbonyl, 3-.4- or 5-isoxazolylcarbonyl, 1.2.3-oxadiazole-4-
or 5-ylcarbonyl, 1,2,4-oxadiazole-3- or 5-ylcarbonyl.

1.2.5-oxadiazole-3- or -4=ylcarbonyl, l, 3.4-oxadiazole-2-
or -5-ylcarbonyl, 2-. 4- or 5-deazolylcarbonyl, 3-. 4- or 5-isodeazolylcarbonyl, 1,2.3-thiadiazol-4- or 5-ylcarbonyl, I, 2°4-thiadiazol-3- or 5-ylcarbonyl, l, 2.5-thianoazole -3- or 4-ylcarbonyl, l, 3.4
-thiadiazol-2- or 5-ylcarbonyl, 2
- or 3-pyrrolinonylcarbonyl, 2-. 3- or 4-pyridylcarbonyl, 2-. 3- or 4-pyridyl-N-oxytocarbonyl, 3- or 4-pyridazinylcarbonyl, 3- or 4-pyridazinyl-N-
oxide carbonyl, 2-. 4- or 5-pyrimidinylcarbonyl, 2-. 4- or 5-pyrimidinyl-N
-oxytocarbonyl, pyrazinylcarbonyl, 2-.
3- or 4-piperidinylcarbonyl, piperanonyl carbonyl, 3H-indol-2- or 3-ylcarbonyl, 2-13- or 4-pyranylcarbonyl,
2-. 3- or 4-thiopyranylcarbonyl, 3-.
4-. 5-. 6-. 7- or 8-quinolylcarbonyl, pyrido[2,3-d]pyrimidinylcarbonyl (e.g.
pyrido[2,3-d]pyrimidin-2-ylcarbonyl), 1.5-, l, 6-, I, 7-1.8-. 2.6-
or 2,7-naphthyridinylcarbonyl (e.g., l, 5
-naphthyridin-2- or 3-ylcarbonyl), cheno[2,3-d]pyridylcarbonyl (e.g. cheno[
2,3-d]pyridin-3-ylcarbonyl), pyrazinoquinolylcarbonyl (e.g., pyrazino[2,3-b]quinolin-2-ylcarbonyl), chromenylcarbonyl (e.g., 2I]-chromene-2 - or 3-ylcarbonyl, etc.) (which may be oxidized),
5- to 6-membered heterocyclic carbonyl groups containing 1 to 4 heteroatoms such as oxygen atoms and sulfur atoms (which may be mono- or dioxidized), 5- to 6-membered heterocyclic acetyl groups (e.g., 2- pyrrolyl acetyl, 3-imidazolylacetyl,
A heteroatom such as a nitrogen atom (which may be oxidized), an oxygen atom, a sulfur atom (which may be mono- or dioxidized) such as 5-isoxacylylacetyl, etc.
5- to 4-membered heterocyclic acetyl groups), etc. are used.

The group represented by the formula -T Qo is specifically, for example, an alkyloxy group, an alkenyloxy group, an aryloxy group, an aralkyloxy group, a tow ring oxy group, an acyloxy group, an alkylthio group, an alkenylthio group, an arylthio group, an aralkyl group. Thio group, heterocyclic thio group, anruthio group, alkyldithio group, aryldithio group, aralkyldithio group, alkylsulfinyl group, alkenylsulfinyl group, arylsulfinyl group, aralkylsulfinyl group, polycyclic sulfinyl group, alkylsulfonyl group, alkenyl A sulfonyl group, an arylsulfonyl group, an aralkylsulfonyl group, a heterocyclic sulfonyl group, etc.

Here, the alkyloxy group (alcoquine group) preferably means a linear, monobranched or cyclic alkyloxy group having 1 to 6 carbon atoms, such as methoxy, ethoxy, n-propoquine, isopropoxy, n-butoxy , isobutoxy, 5ec-butoxy.

tert-butoquino, n-pentyloxy, 5ec-pendeloxy, isopentyloxy, neopentyloxy, cyclopentyloxy, n-hexyloxy, isohexyloxy, cyclohexyloxy, etc. are used,
The alkenyloxy group preferably means a linear tri-branched or cyclic alkenyloxy group having 3 to 6 carbon atoms,
For example, aryluoquine, isobropenyloquine, l-butenyloxy, 2-pentenyloxy, 2-hexyloxy, etc. are used, and the aryloxy group preferably means an aryloxy group having 6 to 14 carbon atoms, such as phenoxy, naphthyloxy , biphenylyloxy, etc., and the aralkyloxy group preferably has 7 to 19 carbon atoms.
means an aralkyloxy group such as benzyloxy, phenethyloxy, phenylpropyloxy, etc., and a heterocyclic oxy group is a group represented by the formula T'-0- (T' represents the above-mentioned heterocyclic group). specifically 2- or 3-pyrrolyloxy, 3-. 4- or 5-
pyrrolyloxy, 2-. 4- or 5-imidazolyloxy.

1.2.3-triazol-4-yloxy, I, 2゜4-triazol-3-yloxy, IH- or 21
-1-tetrazol-5-yloxy, 2- or 3-
furyloxy, 2- or 3-thienyloxy, 2- or 3-thienyloxy-1,1-dioxide, 2-,
4- or 5-oxazolyloxy, etc. are used, and the acyloxy group means a group represented by the formula T″-0- (T″ represents the above-mentioned acyl group), and specifically, acetoxy, propionyl Oxy, butyryloxy, pentanoyloxy, hexanoyloxy, penzylcarbonyloxy, phenylcarbonyloxy, benzoyloxy, naphthoyloxy, thienylcarbonyloxy.

Benzothienylcarbonyloxy, etc. are used, and the alkylthio group preferably means a straight chain monobranched or cyclic alkylthio group having 1 to 6 carbon atoms, such as methylthio, ethylthio, n-provirdio, isopropylthio, n-butylthio. , isobutylthio, 5ec-butylthio, tert-butylthio, n-pentylthio,
5ec-pentylthio, isopentylthio, neopentylthio, cyclopentylthio, n-hexylthio, isohexylthio, cyclohexylthio, etc. are used, and the alkenylthio group is preferably a linear tribranched group having 3 to 6 carbon atoms. means a cyclic alkenylthio group, such as allylthio.

Isopropenylthio, l-butenylthio, 2-pentenylthio, 2-hexenylthio, etc. are used, and the arylthio group preferably means an arylthio group having 6 to 14 carbon atoms, such as phenylthio.

Naphdylthio, biphenylylthio, etc. are used, and the aralkylthio group preferably means an aralkylthio group having 7 to 19 carbon atoms, such as benzylthio, phenethylthio, phenylpropylthio, etc. It means a group represented by T'-9- (T' represents the above-mentioned heterocyclic group), specifically 2- or 3-pyrrolylthio, 3-94- or 5-virazolylthio, 2-
．． 4- or 5-imidazolylthio, l,2.3-triazol-4-ylthio, l,2.4-)lyazol-5-ylthio, lH- or 2H-tetrazol-
5-ylthio, 2- or 3-furylthio, 2- or 3-thienylthio, 2- or 3-thienylthio-1,
1-dioxide, 2-. 4- or 5-oxazolyldio etc. are used, and the anruthio group has the formula T″-8-(T
" means a group represented by the above-mentioned acyl group), specifically acetylthio, propionylthio, butyrylthio, pentanoylthio, hexanoylthio, penzylcarbonylthio, phenethylcarbonylthio, benzoylthio, naphthoylthio, thienylcarbonylthio,
Penzochenylcarbonylthio and the like are used, and the alkyldithio group is preferably a straight chain having 1 to 6 carbon atoms.

means a branched or cyclic alkyldithio group, such as methyldithio, ethyldithio, n-propyldithio,
Cyclobentyldithio, etc. are used, and the aryldithio group preferably means an aryldithio group having 6 to 14 carbon atoms, such as phenyldithio, naphthyldithio, biphenylyldithio, etc., and the aralkyldithio group preferably has a carbon number of 6 to 14. It means an aralkyldithio group having 7 to 19 carbon atoms, such as penzylnotio, phenethyldithio, etc., and an alkylsulfinyl group preferably means a straight chain monobranched or cyclic alkylsulfinyl group having 1 to 6 carbon atoms, such as methyl. Sulfinyl.

Ethylsulfinyl, n-propylsulfinyl, n-
Hexylsulfinyl, cyclohexylsulfinyl, etc. are used, and the alkenylsulfinyl group preferably means a linear monobranched or cyclic alkenylsulfinyl group having 3 to 6 carbon atoms, such as allylsulfinyl, etc. The sulfinyl group preferably means an arylsulfinyl group having 6 to 14 carbon atoms, such as phenylsulfonyl, and the aralkylsulfinyl group preferably means an aralkylsulfinyl group having 7 to 19 carbon atoms, such as benzylsulfinyl. and the heterocyclic sulfinyl group has the formula T'-9O-(
T' means a group represented by the above-mentioned heterocyclic group), specifically 2- or 3-pyrrolylsulfinyl,
3-. 4- or 5-pyrazolylsulfinyl, etc. are used, and the alkylsulfonyl group preferably means a linear, branched, or cyclic alkylsulfonyl group having 1 to 6 carbon atoms, such as methylsulfonyl, ethylsulfonyl, cycloalkylsulfonyl, etc. xylsulfonyl etc. are used, and the alkenylsulfonyl group is preferably a straight chain 1 having 3 to 6 carbon atoms.
Branched means a cyclic alkenylsulfonyl group, such as allylsulfonyl, and the arylsulfonyl group preferably means an arylsulfonyl group having 6 to 14 carbon atoms, such as phenylsulfonyl, naphthylsulfonyl, biphenylsulfonyl, etc. Lylsulfonyl and the like are used, and the aralkylsulfonyl group preferably means an aralkylsulfonyl group having 7 to 19 carbon atoms, such as benzylsulfonyl and phenethylsulfonyl.

A phenylpropylsulfonyl group is used, and the heterocyclic sulfonyl group means a group represented by 2T"-So, - (T' represents the above-mentioned heterocyclic group), and specifically, 2-
or 3-pyrrolylsulfonyl.

3-14- or 5-pyrazolylsulfonyl etc. are used.

Typically, an alkylamino group, preferably a mono- to di(alkyl having 1 to 6 carbon atoms) amino group, such as methylamino, eddylamino, n-propylamino.

rope tylamino, tert-butylamino, n-pendelamino, n-hexylamino, dimethylamino,
diethylamino. Cycloalkylamino groups, preferably mono to di (carbon atoms 3 to 6), such as methylethylamino, di(n-propyl)amino, di(n-butyl)amino
For example, in the cycloalkyl) amino group, fuclopropylamino. An arylamino group, preferably an arylamino group having 6 to 14 carbon atoms, such as cyclopentylamino, cyclohexylamino 1 dicyclohekynylamino, and an aralkylamino group, preferably an aralkyl group having 7 to 19 carbon atoms, such as anilino, N-methylanilino, etc. Amino groups such as pennolamino, 1-phenylethylamino, 2-phenylethylamino, penzhydrylamino, tritylamino, etc., acylamino groups, i.e., formula T''
A group represented by -NH- or (T''), N- (T'' represents the above-mentioned acyl group, and the two groups T'' may form a ring together with a nitrogen atom), specifically: acetamide,
Propionamide, butyrylamino, pentanoylamino, hexanoylamino.

Succinimide, benzylcarbonylamino (pennolcarboxamide), phenethylcarbonylamino (phenethylcarboxamide), benzoylamino (benzamide), naphthoylamino, phthalimide, thienylcarbonylamino (thienylcarboxamide), benzothienylcarbonylamino (penzodienylpoxamide), etc. Alkylcarbonylamino, arylcarbonylamino, heterocyclic carbonylamino (however, the alkyl, aryl, and heterocyclic groups are preferably the same as those mentioned above), cyclic imide, and the like are used.

Specifically, mono- or dialkylsulfamoyl group,
Preferred is a mono- or di(alkyl having 1 to 6 carbon atoms) sulfamoyl group, such as methylsulfamoyl. Ethylsulfamoyl, m-propylsulfamoyl, n-
Hexylsulfamoyl.

Dimethylsulfamoyl, diethylsulfamoyl, methylethylsulfamoyl, di(n-butyl)sulfamoyl, etc., a cycloalkylsulfamoyl group, preferably a cycloalkylsulfamoyl group having 3 to 6 carbon atoms, such as cyclopropyl Arylsulfamoyl groups such as sulfamoyl and cyclohexylsulfamoyl, preferably arylsulfamoyl groups having 6 to 14 carbon atoms,
For example, an aralkylsulfamoyl group such as phenylsulfamoyl, preferably an aralkylsulfamoyl group having 7 to 19 carbon atoms, such as benzylsulfamoyl.

1-phenylethylsulfamoyl, 2-phenylethylsulfamoyl. benzhydrylsulfamoyl, tridelsulfamoyl, etc., an acelsulfamoyl group, ie, a formula T″-NllSOz- or (T″)J-3o! −(
"T" represents the above-mentioned acyl group), for example, acetylsulfamoyl, benzylcarbonylsulfamoyl, thienylcarbonylsulfamoyl, etc. It is represented by 2〇, -3o, -0-. , (specifically, an alkylsulfonyloxy group, preferably an alkylsulfonyloxy group having carbons R1 to 6, such as methanesulfonyloquine.

An arylsulfonyloxy group such as ethanesulfonyloxy, preferably an arylsulfonyloxy group having 6 to 14 carbon atoms, and an aralkylsulfonyloxy group, preferably having 7 to 19 carbon atoms, such as benzenesulfonyloxy, p-toluenesulfonyloxy, etc. Aralkylsulfonyloxy groups such as benzylsulfonyloxy and phenethylsulfonyloxy, and acylsulfonyloxy groups such as acetylsulfonyloquine and butyrylsulfonyloxy are used.

Note that the above-mentioned alkyl group, alkyloxy group (or alkoxy group), alkylthio group, alkyldithio group, alkylsulfinyl group, alkylsulfonyl group, alkylamino group, and cycloalkylamino group.

An alkenyl group, an alkenyloxy group, an alkenylthio group, an alkenyldithio group, an alkenylsulfinyl group, an alkenylsulfonyl group, an alkynyl group, an alkoxycarbonyl group, an alkanoyl group, an alkylsulfonyloxy group further include, for example, an alkylthio group (e.g., methylthio,
Ethylthio, n-propylthio. straight-chain or branched alkylthio groups having 1 to 4 carbon atoms such as isobutylthio),
Halogen atoms (e.g. fluorine, chlorine, bromine, iodine, etc.),
Alkoxy groups (e.g., straight chain or branched alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethyne, n-propoxy, tert-butoxy, n-hexyloxy, etc.),
Nitro group, alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl).

Alkoxy-carbonyl group having 1 to 6 carbon atoms such as isobutoxycarbonyl, 5ec-butoxycarbonyl, tert-butoxycarbonyl), alkylamino 3J, (
For example, methylamino. ethylamino, rhopropylamino, n-butylamino, tert-butylamino, n-
Mono- such as pentylamino, n-hexylamino, dimethylamino, diethylamino, methylethylamino, di(n-propyl)amino, di(n-butyl)amino, etc.
It may be substituted with 1 to 3 g of di(alkyl having 1 to 6 carbon atoms) amino group.

When 2g of alkoxy groups are substituted, 2m of alkoxy groups combine to form, for example, methylenedioxy.

It may also constitute an alkylidene dioxy group having 1 to 3 carbon atoms, such as edgedioquine and propylene diochino, and an alkylidene dioxy group having 2 to 6 carbon atoms, such as ethylidene dioxyquine, propylidene dioxy, and isobropylidene dioxy. .

The above aryl group, aryloxy group, aryloxycarbonyl group, arylcarbonyl group, arylthio group,
Aryldithio group, arylsulfinyl group, arylsulfonyl group, arylamino group.

Aralkyloxy group, aralkyloxocarbonyl group,
Aralkylthio group, aralkyldithio group, aralkylsulfinyl group, aralkylsulfonyl group, aralkylamino group, aralkylcarbonyl group.

The arylsulfonyloxy group and the aralkylsulfonyloxy group further have an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an acyl group, an acyloxy group, a nitro group, an ano group, a halogen, an acylamino group, an alkylthio group, etc. on the aromatic ring. to 3g may be substituted. Here, an alkyl group, an alkenyl group, an alkyl group, an alkoxy group.

The same acyl group, acyloxy group, acylamino group, halogen, and alkylthio group as defined above are used.

When two adjacent alkyl groups are substituted, they may be combined to represent a divalent group such as a trimethylene group or tetramethylene group, and when two adjacent alkenyl groups are substituted, they may be combined to represent a divalent group such as a trimethylene group or a tetramethylene group. propenylene group, 1-
It may also represent a divalent group such as a butenylene group, a 2-butenylene group, or a butadienylene group.

In such a case, the divalent group is further bonded to the fused polycyclic group and 5
~6-membered alicyclic rings (e.g., cyclopentane, cyclohexane,
cyclohexadiene), an aromatic ring (eg, benzene), and a 5- to 6-domain heterocycle containing 1 to 4 heteroatoms (eg, a yellow atom, an oxygen atom, or a nitrogen atom).

Among the above organic residues, preferably (1) a halogen atom,
an alkyl group optionally substituted with 1 to 3 alkylthio groups or alkoxy groups, (2)
Aryl group, (3) alkylthio group.

(4) alkenylthio group, (5) alkylsulfinyl group, (6) alkylsulfonyl group, (7) alkenylsulfonyl group, (8) alkoxycarbonyl group, (9) cal, <moyl group, (10) butadienylene group, (11)
They are an alkylamino group and a (+2) alkoxy group.

The heterocyclic groups of the above-mentioned heterocyclic oxy group, heterocyclic thio group, heterocyclic sulfinyl group, heterocyclic carbonyl group, and heterocyclic sulfonyl group include the above-mentioned alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group, and alkanoyl group. ,
Arylcarbonyl group, alkoxycarbonyl group, aryloquinecarbonyl group, 5-aralkylcarbonyl group, nitro, amino, hydroxy, cyano, sulfamoyl,
Mercapto, halogen atoms (e.g., fluorine, chlorine, bromine,
1 to 3 may be substituted with iodine) or the like.

Particularly preferred substituents on the fused heterocyclic group having an N atom at the substituted bridgehead represented by Q include a halogen atom,
It is a straight chain or branched alkyl group having 1 to 6 carbon atoms or a straight chain or branched alkoxy group having 1 to 6 carbon atoms. Of these, chlorine.

Preference is given to methyl, methoxy, ethoxy or isopropoxy. Particularly preferred is chlorine.

Q is preferably - Shipman [In the above formula, Ro represents a hydrogen atom, a lower alkyl group optionally substituted with a halogen atom, a lower alkylthio group, a lower alkylsulfonyl group, a lower alkoxycarbonyl group, or a halogen atom, , represents a hydrogen atom or a halogen atom, a lower alkokene group, a lower alkylthio group, a lower alkylamino group, a di-lower alkylamino group, X t ,
Each of X 3 represents a hydrogen atom or a lower alkyl group. Among the above, particularly preferred (
a), (b), and (C). No is preferably a halogen atom or a lower alkyl group. X+ is preferably a lower alkoxy group.

Here, a lower alkyl group, a lower alkyl group in a lower alkyl group which may be substituted with a halogen atom, a lower alkyl group in a lower alkylthio group, a lower alkyl group in a lower alkylsulfonyl group, a lower alkyl group in a lower alkylamino group, a di-lower As the lower alkyl group in the alkylamino group, an alkyl group having 1 to 4 carbon atoms (eg, methyl 5-ethyl, rhopropyl, isopropyl, n-butyl, 1-butyl, etc.) is used. As the lower alkoxy group, an alkoxy group having 1 to 4 carbon atoms (eg, methoxy, ethoxy, propoquine, isopropoxy, t-butoxy) is used. As the halogen atom and the halogen atom in the lower alkyl group which may be substituted with a halogen atom, fluorine, chlorine, bromine, etc. are used, and chlorine is particularly preferably used.

The alkyl group represented by Y preferably has 1 to 6 carbon atoms.
means a straight-chain or branched alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 5ec-butyl, tert-butyl,
n-pentyl, 5ec-pendel, isopentyl, neopentyl, n-hexyl, isohexyl, etc. are used,
The halogen atom represented by Yl includes fluorine, chlorine, bromine, iodine, etc., and chlorine is particularly preferred.

The alkyl group represented by R,, R, preferably has 1 carbon number.
means a straight chain tri-branched or cyclic alkyl group of 6 to 6, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, i'tubel, 5ec-butyl, t
ert-butyl, n-pentyl, 5ec-pentyl, isopentyl, neopentyl, cyclopentyl.

n-hexyl, isohexyl, cyclohexyl, etc. are used, and the alkoxy group preferably means a straight-chain or branched alkoxy group having 1 to 6 carbon atoms, such as metquine, ethoxo, n-propoxy, isopropoxy, n- −
butoxy, isobutquin, 5ec-butquin, ter
t-butquine, lobenthyloquine 9n-hequinyloxy etc. are used, and the halogen atoms are fluorine, chlorine, bromine,
Iodine etc. are used.

RI and Rt are each more preferably a lower alkyl group (e.g., a group having 1 to 1 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, etc.).
4 alkyl group) or a lower alkokyne group (e.g., metquine, ethquine, n-propoquine, isobroboxo, n-
Alcoquine groups having 1 to 4 carbon atoms such as butquine and tert-butoxy) or halogen atoms (fluorine.

(chlorine, bromine, etc.). - layer preferably fl, , R2
or a methyl group, a methoxy group, or a chlorine group, respectively. Most preferred is a methyl group or a methoxy group. More preferred is a methoxy group. Z Haniko Mashiwa C1
It is l.

Compounds (1), (It/), and (V) are sulfo groups in the substituent.

It can form inorganic base salts and organic base salts with acidic groups such as carboxyl groups. Also, compound (I), (IT).

(IV) and (V) can form an inorganic acid addition salt or an organic acid addition salt with a basic nitrogen atom in the molecule and a basic group such as an amino group in a substituent. Also, compounds (1), (V)
has an acidic group (-So, NII-C~) in its molecule, so it can form an inorganic base salt or an organic base salt.

Examples of inorganic base salts of compounds (1), (IV), and (V) include salts with alkali gold V4 (e.g., sodium, potassium, etc.), alkaline earth metals (e.g., calcium, etc.), ammonia, etc.; I).

Examples of the basic salts of (IV) and (V) include dimethylamine. Triethylamine, piperazine, pyrrolidine, piperinone, 2-phenylezylbenzylamine,
Salts with pennolamine, ethanolamine, jetanolamine, etc. are used.

Examples of inorganic acid addition salts of compounds (1), (II), (rV), (V) include salts with hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, etc. ), (
As the organic acid addition salts of IV) and (V), for example, salts with p-toluenesulfonic acid, methanesulfonic acid, formic acid, trifluoroacetic acid, etc. are used.

Compounds (1), (n), (IV), (V
) shall also include these salts.

Compound (1) is obtained by reacting compound (TV) and compound (III) in the presence of a base (first step reaction), and then adding compound (II) to the reaction mixture together with an acid under anhydrous conditions. (second stage reaction).

In the first stage of the reaction, compound (III) as a starting material is used in an amount of about 0.5 to 2 times, preferably about 0.8 to 1.2 times, mole relative to compound (■).

In the starting compound (ITI), preferably Y represents a halogen atom or Y represents a phenyl group. Specifically, for example, phenyl chloroformate, methyl chloroformate, ethyl chloroformate, isopropyl chloroformate, diphenyl carbonate,
Dimethyl carbonate, diethyl carbonate, G2
-tolyl carbonate, di-4-tolyl carbonate,
Examples include di(α-naphthyl) carbonate and bis(4-chlorophenyl) carbonate. Preferably phenyl chloroformate is used.

Bases include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal bicarbonates such as sodium hydrogen carbonate, sodium methoxide, sodium ethoxide, and potassium t-butoxide. Such as alcolade, birinone, lutidine. Triethylamine, diisopropylethylamine, tripropylamine, tributylamine, N
, N-thumedelaniline, N,N-diethylaniline,
1,8-noazabicyclo[5,4,0]-7-undecene.

Organic tertiary amines such as 1,4-noazabicyclo[2,2,2]octane are used. Preferred is an organic tertiary amine. Most preferred is triethylamine. The amount of base used is approximately 1 to 2.1 times the mole of compound (III). Specifically, the amount of base is the compound (1'HX
when Y is a halogen atom), about 1.8 to 2.
1 times molar is preferred, and the compound (ITI XY +h'O
It is preferably about 1 to 2.0 times mole relative to Yt) case).

This reaction is carried out in a solvent that does not adversely affect the reaction.

Examples of such solvents include aliphatic hydrocarbons such as petroleum ether, ligroin, and petroleum benzine, aromatic hydrocarbons such as benzene, toluene, and xylene, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, and chlorobenzene. halogenated hydrocarbons,
Diethyl ether, methyl ether, diisopropyl ether, dibdel ether, propylene oxide.

Ethers such as dioxane, tetrahydrofuran, and ethylene glycol monomethyl ether; nitriles such as acetonitrile and propionitrile; ketones such as acetone, methyl isobutyl ketone, and methyl ethyl; esters such as ethyl acetate and butyl acetate. class, tumedelformamide.

Acid amides such as dianoderacetic acid amide, dimethyl sulfokind, sulfolane, and the like are used, preferably halogenated hydrocarbons and nitriles. - Preferably acetonitrile.

It is dichloromethane.

The reaction temperature is about -20°C to 150°C, preferably about 5°C.
to 100°C.

The reaction time is relatively short, usually about 5 minutes to 1 hour.

The reaction is carried out by dissolving compound (1'l/) and a base in a solvent and then adding compound (III) thereto, or by dissolving compound (IV) and (fJJ) in a solvent and then adding a base thereto. .

A compound represented by general formula (V) is obtained in the reaction mixture by this first stage reaction. This product compound (V
) is immediately subjected to the second stage reaction without being isolated from the reaction mixture.

In the second stage of the reaction, the compound ([) is used in an approximately equimolar amount to the compound (IU) used in the first stage reaction. Examples of acids used in the reaction include inorganic acids such as hydrogen chloride, hydrogen bromide, and sulfuric acid, such as methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, and acidic ion exchange resins. Hydrogen chloride, mizuki bromide, etc. may be dissolved in the above-mentioned organic solvent and then used.

Preferred are hydrogen chloride, hydrogen bromide, sulfuric acid, methanesulfonic acid, and ethanesulfonic acid, more preferably methanesulfonic acid. The amount of acid used m varies depending on the amount of base used in the first step reaction and the type of compound ([1). For example, when using compound (III) (when y is a halogen atom), It is preferably about 0.64 to 0.6 times the mole, and when a compound (IIIXY, or OY) is used, it is preferably about 0.9 to 1.1 times the mole based on the base used.

This reaction is carried out under anhydrous conditions. Since water mixed into the reaction solution inhibits the reaction, it is preferable to remove it from the reaction system. The solvent used is the same as that used in the first stage reaction.

This reaction can be carried out by adding acid to the reaction solution obtained in the first stage reaction and then adding compound (II), or by adding compound (IT) and then adding acid, or by adding acid and compound (II). This is done by adding both at the same time.

The reaction temperature runs from about IO to 100°C.

The reaction time varies depending on the reaction temperature, but is usually 10 minutes to 6 minutes.
It takes about an hour. Specifically, the reaction time is as follows: reaction temperature is 50°C.
When the reaction temperature is about 100°C, the reaction time is as short as about 10 minutes to 2 hours, and when the reaction temperature is 10°C or more and less than 50°C, about 1 to 6 hours is required.

The reaction product can be extracted by means known per se, e.g. solvent extraction,
Liquid conversion, distillation, vacuum distillation, vacuum concentration, dissolution.

It can be easily isolated and purified by crystallization, recrystallization, chromatography, etc. Specifically, it can be isolated and purified by an easy method such as cooling the reaction solution and filtering the precipitated crystals, concentrating the reaction solution under pressure, adding a solvent to the residue, and filtering the precipitated product.

Compound (1) can be applied to a wide range of weeds at extremely low doses, such as Japanese grasshopper, Japanese cypress, and Japanese firefly.

Paddy field weeds such as Japanese sagebrush, Japanese grasshopper, Japanese cypress, Japanese cypress, Japanese black bream, Japanese cypress, Japanese thornweed, Japanese azalea, Kikashigusa, Hirumunro, Japanese knotweed, Japanese chickweed, and other rice field weeds. Pigweed, Japanese knotweed, purslane, American king moth, and staghorn moth.

Mulva morning glory, Onamirum, Himeinupie, Okusakibi, Seiban Morokon, Pomfret, and Oat.

Fields of blackgrass, horsetail, chickweed, callana, shrimp grass, chamomile, dayflower, etc.
It not only has excellent grading power against grasses, but also shows high safety with almost no phytotoxicity against crops such as rice, wheat, barley, corn, and soybeans.

Compound (1) shows excellent selective herbicidal effects on crops and various weeds, has low toxicity to mammals, fish and shellfish,
Water Ln without polluting the environment.

It can be used extremely safely as a herbicide in fields, orchards, or non-agricultural fields.

When using Compound (I) as a displacing agent, one or more of Compound (1) may be dissolved or dispersed in a suitable liquid carrier depending on the purpose of use. , or mixed or adsorbed with a suitable solid carrier, emulsion, oil.

Spray, wettable powder, powder, DI, (driftless) type powder.

It is used in preparations such as granules, fine granules, and fine granules F1 tablets. These preparations may contain an emulsifier, a dispersant, a spreading agent, a penetrating agent, a wetting agent, a seminal plasma agent, a stabilizer, etc., as required, and can be prepared by a method known per se. Liquid carriers (solvents) used include, for example, water, alcohols (e.g., methanol, ethanol, n-propanol, isopropanol, ethylene glycol, etc.), ketones (
e.g., acetone, methyl ethyl ketone, etc.), ethers (
For example, dioxane.

tetrahydrofuran, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc.), aliphatic hydrocarbons (e.g. kerosene, kerosene).

fuel oil 1 machine oil, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, solvent naphtha, methylnaphthalene, etc.), halogenated hydrocarbons (e.g., dichloromethane, chloroporum, carbon tetrachloride, etc.), acid amides class (e.g.,
methylformamide, dimethylacetamide F, etc.), esters (e.g., ethyl acetate, butyl acetate, fatty acid glycerol ester, etc.), nitriles (e.g.,
Solvents such as acetonitrile, propionitrile, etc.) are suitable, and these solvents may be used alone or in combination of two or more in an appropriate ratio.

Solid carriers (diluents and bulking agents) include vegetable powders (e.g.
soybean flour, soybean flour, wheat flour, wood flour, etc.), mineral powder (
For example, clays such as kaolin, bentonite, acid clay, and clay, talcs such as talcum powder and waxite powder, silicas such as diatomaceous earth and mica powder, etc.), alumina, sulfur powder, and activated carbon are suitable. They may be used alone or in a mixture of two or more in an appropriate ratio.

Surfactants used as emulsifiers, spreaders, penetrating agents, dispersants, etc. may include soaps, polyoxygen/ethylene alkylaryl ethers (e.g., Neugen, E-Ni 142 (E, Al42)) as necessary. o Daiichi Kogyo Seiyaku Co., Ltd.), polyoxyene, tyrene aryl esters (e.g., nonal, manufactured by Toho Chemical Co., Ltd.), alkyl sulfates (e.g., Emar o)
0 10, Emar 40, manufactured by Kao Soap Co., Ltd.), Arya, I2. ．． 1. , acid salts (e.g., Neoge, ■, Ohgea, T, Daiichi Kogyo Seiyaku Co., Ltd., Neobere Sis 0, Kao Soap Co., Ltd.), polyethylene glycol ethers (e.g., Noniball 85, Noniball 100, Noniball 1)
Nonionic and anionic surfactants such as Tween 2oo, To, and Vienna 80 (manufactured by Kao Soap Co., Ltd.) are used.

The appropriate content ratio of the compound (D) in the herbicide is about 1 to 90% by weight for emulsions, hydrating agents, etc., and for oils, powders, DL
(Driftless) 0.01 to 10 for mold grinding, etc.
Fine granules F are suitable for a heavy claw shape.

The appropriate concentration for granules is about 0.05 to 10% by weight, but these concentrations may be changed as appropriate depending on the purpose of use. Emulsions, wettable powders, etc., are diluted appropriately with water (for example, 100 to 100,000 times) before use, and then dispersed.

When using compound (1) as a herbicide, does it vary depending on the application situation, application period, application method, target grass species, cultivated crops, etc.?In general, the amount used as an active ingredient (compound (I)) per 1 are of paddy field. About 50g from 005, preferably about 5g from 061, about 005 to 20g per 1 area of farmland.
The amount is approximately 0.1 to 5 g, preferably approximately 0.1 to 5 g.

Compound (1) is suitable for use as a pre-emergence soil treatment or a foliage and soil treatment agent for paddy field weeds.

For example, herbicides can be safely used immediately after rice transplantation or even 2 to 3 weeks after rice transplantation without causing substantial chemical damage, and their effects persist over a long period of time.

Herbicides include other types of herbicides, plant growth regulators, fungicides (e.g., organochlorine fungicides, organic fungicides, azole fungicides, antibiotics, etc.), and insecticides (e.g. , pyrethroid insecticides, organophosphate insecticides.

Carbamate insecticides, etc.), other acaricides, 3-stage nematode agents, synergists, attractants, repellent 2-colors, fertilizers, etc. can be mixed and used.

Compound (H) as a raw material compound used in the method of the present invention.

(III) and (■) are known or can be easily produced from known compounds.

For example, compound (II) is
of Heterocyclic Compounders (Interscience Publishers New York-London) [The Chemistry ofllet
erocyclic compounds (Inte
rsciencePublishers, New Y
ork & London)] 16th L 19
1962, Journal or Organic Chemistry
emistry) No. 28Q, pp. 1812-1821 (1
963) or a chapter thereof.

Compound (IV) can be prepared by the following reaction schemes (+) to (
It can be easily produced by producing compound (VT) or its salt according to 4), and then reacting compound (Vl) or its salt with ammonia.

Method (1) Method (2) Method (3) Method (4) [In the formula, Hal is a halogen atom, and R5° is a hydrogen atom.

Bennol group or S-Q, other symbols have the same meanings as above] The halogen atom represented by Hal is fluorine.

Chlorine, bromine, etc. are used.

The compound represented by the above formula may be used as the above-mentioned base salt or acid addition salt.

Specific examples of the above method (1) include, for example, [the symbols in the above formula do not have the same meanings as above].

As a specific example of the above method (2), [Symbols in the formula have the same meanings as above] etc. can be mentioned.

A specific example of the above method (3) is, for example, [the symbols in the above formula have the same meanings as above].

A specific example of the above method (4) is as follows: [Symbols in the two notations have the same meaning as the notations].

Method for producing the above compound (Vl) or its salt (1)
All reactions included in (4) are reactions that are known per se,
For example, the MeLhoden der Organische
9 (1955), Sulfonation and Related Reactions (Interscience Publishers New York) [5.
Reacted Reactions (Inte
rsciencc Publishers, Ne
w York)] (11965, Sy
nthesis) + 969.

3~! It can be carried out by the method described in JP-A No. 60-208977, page 0, or in accordance with those methods.

For example, compound (Vl) or a salt thereof can be produced by the following method.

Method (1) In the sulfonation reaction, for example, sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, etc. are used as the sulfonating agent. The sulfonating agent is used in an amount of about 0.8 to 3 times the mole of Compound Q-11 or its salt as a raw material. This reaction involves carbon disulfide, chloroform, carbon tetrachloride, tetrachloroethane,
It is carried out in an inert solvent such as chlorobenzene. In particular, good results are often obtained by using chlorosulfonic acid in chloroform. The reaction temperature is about O~200
℃, preferably about 20-120℃. The reaction time is about 20 minutes to several days. In the halogenation reaction of compound Q-S03H or a salt thereof, a chlorinating agent such as thionyl chloride, phosphorus oxybromide, or a brominating agent such as thionyl bromide or phosphorus oxybromide is used.

The halogenating agent is about 0.8 for compound Q-3O,H.
~10 times the molar amount is used. The yield may be improved if the reaction is carried out in the presence of pyridine, triethylamine, tri-n-propylamine, N,N-trimethylaniline, or the like.

The reaction temperature is about 20-120°C. The reaction time is about 30 minutes to 20 hours.

Method (2) In the diazotization reaction of compound Q N11 or a salt thereof, compound Q -N Ht as a raw material is mixed with sodium nitrite in hydrochloric acid under normal diazotization conditions, for example, under cooling to about -20 to 10°C. React with diazonium salt Q N
2"Hal"".

This diazonium salt is then reacted with sulfur dioxide in the presence of a copper halide, such as cuprous chloride or cupric chloride, to produce compound (Vl) or a salt thereof.

Copper halide is about 0.01 to 3 to diazonium salt
Use twice the mole. Sulfur dioxide is used in a molar amount of about 0.8 to 3 times that of the diazonium salt, but may be used in large excess.

This reaction is carried out under acidic conditions. The reaction temperature is about -20
° to +00°C. The reaction time is about 30 minutes to 12 hours.

Method (3) This method uses compound Q-5 substituted with a group containing divalent sulfur.
Fl, or a salt thereof is oxidatively halogenated (for example, chlorinated) in the presence of water to lead to a compound (Ml) or a salt thereof. Examples of halogenating agents include chlorine monosodium hypochlorite, potassium hypochlorite, N-[10]succinimide, and the like.

Bromine etc. are used. The halogenating agent is the Q of the raw material compound.
-911,a or its salt is used in about 1 to 10 times the molar amount. This reaction is preferably carried out under acidic conditions by adding hydrochloric acid, acetic acid, etc. The reaction temperature is about -10 to 30°C. The reaction time is about 30 minutes to 5 hours.

Method (4) This method replaces the heterocyclic hydrogen (e.g. imidazole ring hydrogen) of the compound Q-H or its salt with lithium, and then reacts it with sulfur dioxide to form the sulfinate lithium compound Q-
9o, Li is obtained and then treated with a halogenating agent such as a chlorinating agent to lead to compound (VI) or a salt thereof. As the lithiation agent used in the reaction for producing compound Q-9od, i or its salt, methylridium, n
-Alkyl lithium such as butyl lithium and L-butyl lithium.

Examples include lithium amide and lithium diisopropylamide. The lithiation agent is used in a molar amount of about 1 to 3 times the amount of the starting compound Q-[or its salt].

Sulfur dioxide is used in about 1 to 5 times the molar amount. The reaction temperature is about -70 to 50°C. The reaction time is about 1 to 20 hours.

Next, as a halogenating agent used in the halogenation reaction of the compound Q-SO, Li or its salt, for example, chlorine 1
Examples include chlorinating agents such as N-chlorosuccinimide. Compound (Vl) or a salt thereof thus obtained can be reacted with ammonia to lead to compound (IV) or a salt thereof. In the reaction of compound (Vl) or its salt with ammonia, ammonia reacts with compound (Vl)
) or its salt is usually used in an amount of 0.8 to 10 mol. This reaction usually uses water, ether, THF, and acetonitrile.

It is carried out in an inert solvent such as alcohol (eg, methanol, ethanol), dichloromethane, chloroform, etc. The reaction temperature is about -60 to 100°C. The reaction time is about 30 minutes to 8 hours.

Compound (IV) or a salt thereof can also be produced according to the following reaction scheme.

[Symbols in the formula have the same meanings as above] -Funzo Q -S I- [Symbols in the formula have the same meanings as above] Examples of the compound include [Symbols in the formula do not have the same meanings as above].

The first step is carried out by reacting the compound (■) or its salt with chlorine or sodium hypochlorite in aqueous ammonia.

This reaction was performed using a method called Methoden der Organischen.
En Chemie) Vol. 9, 277-278.

Step 2] The second step is carried out by oxidizing the obtained compound (■) or its salt with an oxidizing agent.

Oxidizing agents include hydrogen peroxide, potassium permanganate,
Metachloroperbenzoic acid or the like should be used.

The amount of oxidizing agent used in this reaction may be the amount m necessary to complete the reaction, but theoretically, 2 equivalents of active oxygen should be used per mole of the starting compound (■) or its salt. It is sufficient to use the amount that generates .

The reaction is generally carried out in a solvent that does not adversely affect the reaction. Suitable solvents include solvents inert to the reaction, such as water, methanol, ethanol, n-propanol, isopropanol, n-butanol.

Alcohols such as tert-butanol, benzene.

Aromatic hydrocarbons such as toluene, xylene, nitrobenzene, and chlorobenzene, halogenated hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride, and the like are used.

The reaction temperature can be selected from a range of about -60 to 100°C at which the reaction proceeds, but generally about -20 to 50°C is suitable. The reaction time is relatively short, about 5 minutes to 2 hours.

Furthermore, compound (rV) can be produced by the following method.

Furthermore, as shown in the reaction scheme below, the substituent in compound (■) can be easily converted to another type of substituent.

The raw material compounds Q H, Q-NHt, Q SR+o and their salts were obtained from The Chemistry of Heterocyclic Compounds (The Chemistry of Heterocyclic Compounds).
Terocyclic Compounds (In
tersciencePub I jshers)] Part 15@, Part I (Part I) and Part 2
(Part 2), Volume 30, Comprehensive Heterocyclic Chemistry (Pergamon 0 Press)
yclicChemistry (Pergamon
Press) Volumes 4 and 5.

Liebigs Annaren der Hemi (1, ie
bigs Annalen der Chemi
c) Vol. 663, pp. 113-117 (1963), 6
Volume 47, page 138 (1961), Journal of Organic Chemistry
Organic Chemistry) Volume 49,
3534 pages (1984), volume 38 +955 (19
1973), Vol. 36, p. 11 (1971), No. 3
Volume 0, page 4081 (1965), Volume 30, 240
3 pages (1965), Journal of Heterocyclic Chemistry (Journal of I
leterocyclicCbemistry), 2nd
Volume, page 53 (1965), Volume 5.

695 pages (1968), Journal of Mesoisonal Chemistry Uownal or Med
icinalChemistry) Volume 12, 10
31 pages (1969).

Volume 15, pages 415 and 982 (1972), Volume 20
Vol. 387 (1977), Vol. 21, p. 235 (1977)
978), Journal of the Chemical Society
micalSociety) l 946, 1075
Page, same 1955.

2834 pages, 1963, 3277 pages, Chemical and Pharmaceutical Bulletin (Chem
ical and pharmaceutical
Bulletin) Volume 11, +564 pages (196
3rd year), Volume 12.

p. 813 (1964), vol. 22, p. 482 (197
4), Pharmaceutical Journal, Volume 91, +154 pages (1971)
, vol. 94, p. 839 (1974).

Volume 98, page 631 (1978), Gazzetta Chmica Italiana
Italiana) Vol. 105, p. 777 (1975), Chemical Abstracts (Chemical
Abstracts) Volume 72 216696 (19
1970), vol. 50, 313 (1956), vol. 73 87855 and + 20548p (1970), 8
Volume 8.

22752r (1978), U.S. Patent 3901903
, Special Publication No. 44-32793. Farmaco Ediz
ion 5 scientifica) Volume 36.

994 (1981), or according to the method described therein.

The manufacturing method of representative compounds among these raw material compounds will be described below.

(Margin below) θ g9
e −Φ
G Q: ″[Stock]■ [Phase] [In the above formula, R1 is an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, or propyl, a hydrogen atom, or a hydroxyl group, and R1 is, for example, methyl, ethyl, or propyl. ] In the above reaction, for example, the reaction shown for imidazo[1,2-a]pyridine is imidazo[1,2-a]pyrimidine, imidazo[1,2 -a] pyrazine, imidazo [
1,1-b]pyridazine, imidazo[1,2-b(1
,2,4) triazine, imidazo[1,2-a]imidazole, imidazo[1,2-b]pyrazole, imidazo[2,j-b]thiazole, imidazo[2,1-b](
1.

3.4) Can be carried out in the same way for other fused imidazoles such as deadiazole (same as for other fused heterocycles)
.

(Effects of the Invention) According to the method of the present invention, compound (1) can be easily produced from readily available raw materials with good yield and high purity.

The reaction operation is simple and the reaction time is short from one reaction step, making it extremely useful as an industrial production method.

The present invention will be specifically explained below by showing Reference Examples, Examples, and Formulation Examples.

Symbols in Reference Examples and Examples have the following meanings.

S: singlet, d, doublet, t nitribulet, q, quartet, d, d: double doublet.

m: multibullet, br: broad, J: coupling constant, DMSO dimethyl sulfokide % indicates weight % unless otherwise specified. Room temperature usually refers to about 10 to 30°C.

(Left below) Reference Example 1 2-chloroimidazo[1,2-a]pyridine-3-sulfonic acid 3.5 g of 2-chloroimidazo[1,2-a]pyridine was dissolved in 20+nl of chloroform, and chlorosulfone acid 4
．． A solution prepared by dissolving 6 ml in 10 ml of chloroform was added dropwise over 20 minutes. The reaction solution was heated and refluxed for 6 hours with stirring to produce a viscous oil. The supernatant liquid is removed, ether and a small amount of ethanol are added, and the precipitated crystals are collected by filtration and dried to obtain 5.1 g of the 172 permanent product of the title compound.

NMR (DMSO-d,) δ: 7.21-7.45
(m, IH).

7.62-7.80 (+n, 2H), 8.9 (d, I
H), 9.4(s, 2H) Reference Example 2 2-chloroimidazo[1,2-a]pyridine-3-sulfonyl chloride 2-chloroimidazo[1,2-a]pyridine-3-sulfonic acid5. 0g was suspended in 30ml of phosphorus oxychloride,
Heat to reflux for an hour. After cooling, the reaction solution was poured into 250 ml of ice water and extracted with dichloromethane. The dichloromethane layer was separated, dried over anhydrous sodium sulfate, and dichloromethane was distilled off under reduced pressure to obtain 4.6 g of the title compound as pale yellow crystals.

NMR(CDCls)δ: 7.2-7.4(
m, 11ri, 7.6-79 (m, 211), 8.8
5(d, 111) Reference Example 3 2-chloroimidazo[1,2-a]pyridine-3-sulfonamide 2-chloroimidazo[1] was added to 60 ml of aqueous ammonia under cooling.
,2-a]pyridine-3-sulfonyl chloride 4.6
Add a solution of g in 60n+1 acetonitrile, and stir at room temperature for 2 hours. Distill the acetonitrile under reduced pressure,
The precipitated crystals are collected by filtration and washed with water to obtain 3.8 g of the title compound. Recrystallization from dilute ethanol gives colorless needle-shaped crystals.

mp, 175-177°C N M n (DM S Od8) δ: 7.2-
7.45 (m, III), 7゜5~7.9 (m, 21
1), 8.15 (s, 211), 8. H(d, 1I
I) The following compounds can also be produced by the method described in Japanese Patent Application No. 62-56250.

(6-methylimidazo[2,1-b]thiazole-5
-Sulfonamide (2) 2-chloro-6-methylimidazo[+, 2-b
] Pyridazine-3-sulfonamide N M R (DM S Oda) δ 4.05 (s,
3H), 7.16 (d, III), 7.75 (s,
211), 8.11(d, 1ll) (3) 2-chloro-6-nitoquine imidazo[1,2-b]pyridazine-3
-Sulfonamide (4) 2-chloro-6-(n-propoquino)imidazo[
1,2-b]pyridazine-3-sulfonamide (Example) Example 1 N-(2-chloroimidazo[1,2-a]pyrinone-3
-ylsulfonyl)-N'-(4,6-dimethoxy-2
-pyrimidinyl) urea (compound No. 1) 2-chloroimidazo[1,2-al pyridine-3-sulfonamide 2
．． 32 g (0.01 mol) and triethylamine 2.02
g (0.02 mol) was dissolved in 30% acetonitrile,
1.60 g (0.01 mol) of phenyl chloroformate are added with stirring at 10-20°C. 20~25°C
After stirring for 30 minutes, add 1.00 g of methanesulfonic acid.
(0.010 mol) and 1.55 g (0.01 mol) of 2-amino-4,6-simethoxypyrimidine are added in this order and stirred at 600C for 15 minutes. The reaction solution is cooled, and the precipitated crystals are collected by filtration and washed three times with water. The resulting crystals are dried over PtOs under reduced pressure to obtain 3.42 g (yield: 83.0%) of the title compound. -mp,
183-184°C (dec,) NMR (DMSO-d
, δ3.95(s, 611), 6.0(s, 111
), 7.3-7.5 (m, III), 7.5-7.
9 (m, 2tl) 8.97 (d, III), 10.6
5(s, 1ll), 12.8(s, III) Example 2 N-(2-chloroimidazo[1,2-a]pyridine-3
-ylsulfonyl)-N'-(/L, 6-diphthoquine-2-pyrimidinyl)urea (Compound No. 1) 2-chloroimidazo[1,2-a]pyridine-3-sulfonamide 10. Og (0,043 mol) and triethylamine 8
．． 85 g (0,0866 mol) of dichloromethane 200
In addition to the mixture, 6.78 g (0,0433 mol) of phenyl chloroformate was added dropwise while stirring at 20-25°C. After stirring at the same temperature for 30 minutes, 4.20 g (0,0433 mol) of methanesulfonic acid and 2-amino-4
, 6-nomethoxypyrimidine 6.72g (0,0433
mol) in this order and reflux for 5 hours. After the reaction, dichloromethane was removed under reduced pressure and acetonitrile 5
Add zero precepts and filter the precipitate. Acetonitrile IOd
After washing three times with water, the resulting crystals were washed with P, 0. When dried under reduced pressure above, 15.62 g (yield 87.9%) of the title compound was obtained.
is obtained.

mp, 183-184°C (dec, ) The compounds obtained in the same manner as above are shown in Table I.

(The following is a blank space) Table 1 Not only the above-mentioned compounds but also various compounds described in Japanese Patent Application No. 62-56250 are produced in good yields by the same procedure as in Examples 1 and 2 above.

Formulation Example I Emulsion Compound No. 1 An emulsion containing 2% by weight of xylene, 75% by weight of dimethylformamide, 18% by weight of polyethylene glycol ether (Nonibol 85) and 5% by weight. (Used after diluting appropriately with water) Formulation Example 2 Wettable powder Compound No. 3 5% by weight Sodium lignin sulfonate 5% by weight Polyoquine ethylene glycol ether (Noniball 85)
5Xπview% clay
80 city M% white carbon 5 weight q%
A hydrating agent made by mixing and pulverizing ゛. (Use after appropriately diluting with water) Formulation example 3 Preparative agent compound No. 2 0.25% by weight
Sodium ligninsulfonate 2% by weight Bentonite 57.75% by weight Talc
Granules made by adding water to a 40% by weight mixture and kneading and granulating it.

Formulation Example 4 Granules Granules made by adding water to a mixture of Compound No. I O, 25% by weight sodium ligninsulfonate, 5% by weight bentonite and 94.75% by weight, and kneading and granulating the mixture.

Formulation Example 5 Granules Compound No. 2 Granules made by adding water to a mixture of 93.5% by weight of 0.5% by weight sodium ligninsulfonate, 6.0% by weight bentonite, and kneading the mixture for granulation.

Formulation Example 6 Granule Compound No. I O, 25% by weight Sodium ligninsulfonate 5% by weight Bentonite 30.00% by weight Clay
Granules made by adding water to a 64.75% by weight mixture and kneading and granulating it.

Test Example 1 Selectivity test for rice A 150 cm square plastic pot was filled with rice paddy soil, and after being soaked in water for 1 generation, seeds of Japanese millet and Japanese cypress were sown. Cultivate at a depth of 3 cm for a specified period of time.Meanwhile, fill a 1/10,000 Ahl Wagnerbot with paddy soil, and after 9 generations of watering, transplant two paddy seedlings and submerge them to a depth of 3 cm.One day after transplanting the paddy rice, a single leaf of monocotyledonous weeds appears. When the period has been reached, a diluted drug solution containing compound (I) is applied to the pot so that Ig per are.The diluted drug solution is compound (1) Ig total surfactant twin 202. %(W/
v) in 300 ml of acetone and diluted with water to give a total of J; t40Q.

Three hours after the chemical treatment, the herbicidal effect on various weeds and the chemical damage to paddy rice were evaluated according to the following criteria.

Index Effect Suppression rate (weed killing rate)%0
No O! Fine 0.1~502
Small 50.1-753 Medium
75.1~87.54 Large
87.6 to 99.95 Extremely thick 100 W The drug damage is expressed by the following index (the same applies to the following test examples).

Index Drug damage Damage rate % 0 None 0 1 @ 0.1~12.52
Small 12.6-253 Medium
25.1-50.04 Dog
50.1 to 99.9 results are shown in Table 2.

It is clear that the compound (1) obtained by the method of the present invention has no phytotoxic effects on rice and exhibits an excellent herbicidal effect on rice.

Agent Patent Attorney Iwa 1) Hiroshi

Claims (1)

[Claims] A compound represented by the general formula Q-SO_2NH_2 [wherein Q represents a condensed heterocyclic group having an N atom at the bridgehead which may have a substituent] and the general formula ▲Mathematical formula, chemical formula , tables, etc.▼ [In the formula, Y_1 is a halogen atom or -OY_2, Y
_2 represents an alkyl group or a phenyl group] in the presence of a base, and then the reaction mixture is subjected to anhydrous conditions to form a compound represented by the general formula ▲ mathematical formula, chemical formula, table, etc. ▼ [wherein, R_1 and R_2 each represent an alkyl group, an alkoxy group, or a halogen atom, and Z represents CH or N] A general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ The symbols in the formula have the same meanings as above].