JPH04128269A - Sulfamidesulfonylurea derivative and herbicide - Google Patents

Abstract

NEW MATERIAL:Compounds of formula I [Q is formula II or III (R<11> is alkyl, cycloalkyl, phenyl, etc.; R<12> is H, alkyl, alkenyl, etc.; R<13> is alkyl, phenyl or benzyl; R<21> is alkyl, cycloalkyl, phenyl, etc.; R<22> and R<23> are H or alkyl; R<24> is H, alkyl, halogen, etc.), etc.; L is H, alkyl, alkenyl, etc.; X is O or S; G is formula IV (A is CH or N; B and C are alkyl, alkoxy, halogen, etc.)] or derivatives thereof. EXAMPLE:1-[(N-dimethylsulfamoyl-N-methoxy-amino)sulfonyl]-3-(4,6- dimethoxypyrimidin-2-yl)urea. USE:A herbicide having a selectivity to important crops. PREPARATION:For example, a sulfamidesulfonyl iso(thio)cyanate derivative of formula V is made to react with pyrimidine of formula VI or a triazine derivative to obtain the objective compound of formula I.

Description

[Industrial application field]

The present invention relates to novel sulfamide sulfonylurea derivatives and herbicides containing them as active ingredients. [Prior Art and Problems] The use of herbicides is essential to protect important crops such as rice, wheat, corn, soybeans, cotton, and beets from weed damage and to increase yields. Particularly in recent years, there has been a demand for selective herbicides that can selectively kill only weeds without causing chemical damage to crops even when applied to the foliage of crops and weeds simultaneously in cultivated land where these useful crops and weeds coexist. ing. In addition, from the viewpoint of preventing environmental pollution and reducing economic costs during transportation and spraying, search research has been carried out for many years to find compounds that have a high herbicidal effect with as low a dose as possible. Although some compounds with these properties are currently used as selective herbicides, there remains a need for new and better compounds with these properties. As a prior art with a structure similar to the compound of the present invention, a compound in which a sulfonylurea is bonded to a nitrogen atom is disclosed in JP-A-58
It is disclosed in Japanese Patent Application Laid-open No. 103371, Japanese Patent Application Laid-Open No. 60-48973, and Japanese Patent Application Laid-Open No. 151577/1999. JP-A-60-48973 and JP-A-1-1515
No. 77 discloses a compound in which a sulfonylurea is bonded to a nitrogen atom in a sulfonamide structure, but a compound in which a sulfonylurea is bonded to a nitrogen atom in a special sulfamide structure, such as the compound of the present invention, has never been known. First, it is a new compound. [Means for solving the problem] In order to develop herbicides that are selective for important crops, the present inventors have continued research for many years to develop compounds with higher herbicidal power and selectivity. We have investigated the herbicidal properties of many compounds. As a result, the general formula (I): R”-S Q!!, R” is an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 3 to 6 carbon atoms.
7 cycloalkyl group, cycloalkenyl group having 3 to 7 carbon atoms, alkyl group having 1 to 6 carbon atoms substituted with a cycloalkyl group having 3 to 7 carbon atoms, monomer having 3 to 7 carbon atoms - or an alkyl group having 1 to 6 carbon atoms substituted by an alkenyl group having 2 to 6 atoms, an alkynyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms substituted with a polyhalogenocycloalkyl group. C1-C6 alkyl group substituted with a C1-C6 alkylthio group; C1-6 alkyl group substituted with a C1-C6 mono- or dialkylamino group; Alkyl group, mono- or polyhalogenoalkyl group having 1 to 6 carbon atoms, having 2 to 6 carbon atoms
A mono- or polyhalogenoalkenyl group, an alkyl group having 1 to 6 carbon atoms substituted with a cyano group, an alkyl group having 1 to 6 carbon atoms substituted with an alkoxycarbonyl group having 1 to 6 carbon atoms, carbon Number of atoms 1-6
an alkenyl group having 2 to 6 carbon atoms substituted with an alkoxycarbonyl group, and an alkenyl group having 1 to 6 carbon atoms substituted with an alkoxycarbonyl group having 1 to 6 carbon atoms;
6 mono- or polyhalogenoalkyl group, an alkyl group having 1 to 6 carbon atoms substituted with a mono- or dialkylaminocarbonyl group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, a C1-6 alkyl group substituted by a C1-6 mono- or dialkyl-minocarbonyl group, a cyano group, a C1-6 alkylcarbonyl group;
C1-60 alkylcarbonyl group, C1-6 mono- or polyhalogenoalkylcarbonyl group, phenyl group and benzyl group (however, these phenyl groups and benzyl groups are halogen atoms, trifluoromethyl groups, (Optionally mono- or polysubstituted with a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkoxycarbonyl group having 1 to 6 carbon atoms), 3 to 6 member heterocycle (However, these heterocycles contain 1 to 3 heteroatoms selected from nitrogen atoms, oxygen atoms, or sulfur atoms in the ring. These heterocycles also include halogen atoms, tricarbon atoms, fluoromethyl group,
It may be mono- or polysubstituted with a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkoxycarbonyl group having 1 to 6 carbon atoms. ), a 3- to 6-membered heterocycle (however, these heterocycles contain 1 to 3 heteroatoms selected from nitrogen atoms, oxygen atoms, or sulfur atoms in the ring. , halogen atom, trifluoromethyl group, nitro group, alkyl group having 1 to 6 carbon atoms, 1 to 6 carbon atoms
may be mono- or polysubstituted with an alkoxy group or an alkoxycarbonyl group having 1 to 6 carbon atoms. ) represents an alkyl group having 1 to 6 carbon atoms, and R1! is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
Alkenyl groups having 2 to 6 carbon atoms, alkynyl groups having 2 to 6 carbon atoms, phenyl groups and benzyl groups (however, these phenyl groups and benzyl groups are halogen atoms, trifluoromethyl groups, 1 to 6 carbon atoms) (optionally substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkoxycarbonyl group having 1 to 6 carbon atoms. Phenyl group and benzyl group (however, these phenyl group and benzyl group include halogen atom, trifluoromethyl group, alkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, and 1 to 6 carbon atoms) may be substituted with an alkoxycarbonyl group or a nitro group), or R'2 and R1'' represent a saturated 5- to 7-shell heterocycle together with the nitrogen atom to which they are bonded, Alternatively, R'2 and R'' together with the oxygen and nitrogen atoms to which they are bonded represent a saturated 5- to 7-membered heterocycle, and R'' is an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms; 3～
7 cycloalkyl group, a C1-6 alkyl group substituted with a C3-7 cycloalkyl group, a C1-6 alkyl group substituted with a C3-7 mono- or polyhalogenocycloalkyl group Number of carbon atoms: 1-6
an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with an alkoxy group having 1 to 6 carbon atoms, a carbon atom An alkyl group having 1 to 6 carbon atoms substituted with an alkylthio group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with a mono- or dialkylamino group having 1 to 6 carbon atoms, Number of carbon atoms: 1
~6 mono- or polyhalogenoalkyl groups, mono- or polyhalogenoalkenyl groups having 2 to 6 carbon atoms, alkyl groups having 1 to 6 carbon atoms substituted with cyano groups, and C1 to 6 alkyl groups having 1 to 6 carbon atoms An alkyl group having 1 to 6 carbon atoms substituted by an alkoxycarbonyl group, an alkenyl group having 2 to 6 carbon atoms substituted by an alkoxycarbonyl group having 1 to 6 carbon atoms, 1 carbon atom
an alkyl group having 1 to 6 carbon atoms substituted with ~6 mono- or dialkylaminocarbonyl groups, an alkoxycarbonyl group having 1 to 6 carbon atoms, 1 carbon atom
~6 mono- or dialkylaminocarbonyl groups, cyano groups, alkyl groups having 1 to 6 carbon atoms substituted with alkylcarbonyl groups having 1 to 6 carbon atoms, alkylcarbonyl groups having 1 to 6 carbon atoms, Number of carbon atoms l~
6 mono- or polyhalogenoalkylcarbonyl group,
Phenyl group and benzyl group (However, these phenyl group and benzyl group include halogen atom, trifluoromethyl group, nitro group, alkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, and may be mono- or polysubstituted with 1 to 6 alkoxycarbonyl groups), 5 to 6-membered heterocycles (provided that these heterocycles are nitrogen atoms, oxygen atoms, or sulfur atoms). The ring contains 1 to 3 heteroatoms.These heterocycles include halogen atoms, trifluoromethyl groups, nitro groups, alkyl groups having 1 to 6 carbon atoms, and 1 to 3 carbon atoms.
It may be mono- or polysubstituted by an alkoxy group having 6 or an alkoxycarbonyl group having 1 to 6 carbon atoms. ), R" represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R1' represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Rt< represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. an alkyl group having 1 to 6 atoms,
a halogen atom, a mono- or polyhalogenoalkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms; C1-6 alkyl group substituted with oxy group, C2-6 alkyl group
an alkyl group having 1 to 6 carbon atoms substituted with an alkynyloxy group, an alkyl group having 1 to 6 carbon atoms substituted with a mono- or polyhalogenoalkoxy group having 1 to 6 carbon atoms, a carbon atom An alkyl group having 1 to 6 carbon atoms substituted with an alkylthio group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted by an alkylsulfonyl group having 1 to 6 carbon atoms, and a cyano group. A substituted alkyl group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted by an alkoxycarbonyl group having 1 to 6 carbon atoms, Number of carbon atoms: 1-6
represents an alkyl group having 1 to 6 carbon atoms substituted with an alkylcarbonyl group having 1 to 6 carbon atoms, and R'' is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
R'' represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R27 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R1' is a hydrogen atom , an alkyl group having 1 to 6 carbon atoms,
A mono- or polyhalogenoalkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted by an alkoxy group having 1 to 6 carbon atoms, 2 to 6 carbon atoms
an alkyl group having 1 to 6 carbon atoms substituted with an alkenyloxy group, an alkyl group having 1 to 6 carbon atoms substituted by an alkynyloxy group having 2 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms substituted with an alkenyloxy group having 1 to 6 carbon atoms; an alkyl group having 1 to 6 carbon atoms substituted with an alkylthio group having 1 carbon atom
an alkyl group having 1 to 6 carbon atoms substituted with an alkylsulfonyl group of ~6, an alkyl group having 1 to 6 carbon atoms substituted by a cyano group, and an alkyl group having 1 to 6 carbon atoms;
an alkoxycarbonyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with an alkoxycarbonyl group having 1 to 6 carbon atoms, an alkylcarbonyl group having 1 to 6 carbon atoms; represents an alkyl group having 1 to 6 carbon atoms substituted by a group, and L represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms. represents an alkynyl group, X represents an oxygen atom or a sulfur atom, A represents a CH group or a nitrogen atom, and B and C each independently represent an alkyl group having 1 to 4 carbon atoms; an alkoxy group having 1 to 4 carbon atoms, a mono- or polyhalogenoalkyl group having 1 to 4 carbon atoms, a mono- or polyhalogenoalkoxy group having 1 to 4 carbon atoms, a halogen atom, a monoalkyl group having 1 to 4 carbon atoms, a mono- or polyhalogenoalkyl group having 1 to 4 carbon atoms, represent. ] Sulfamide sulfonylurea derivatives and their agriculturally suitable salts (hereinafter referred to as
The compound of the present invention) has an extremely strong herbicidal power against many weeds in both soil treatment and foliage treatment, and is effective against important crops such as wheat, corn, cotton, soybean, beet, etc. The present invention was completed by discovering that this product has high safety against rice and the like. On the other hand, the compounds of the present invention exhibit high herbicidal activity at a much lower dose than conventional herbicides, and are therefore useful as herbicides for orchards and non-agricultural lands. The compound of the present invention represented by general formula (I) is represented by the following reaction formula 1.
-6 can be easily manufactured. Reaction formula 1 (I) [In the formula, Q, G, L and X have the same meanings as above. ] That is, sulfamide sulfonyl iso(thio)cyanate derivative (II) is dissolved in a sufficiently dried inert solvent such as dioxane, acetonitrile, acetone, etc., and a pyrimidine or triazine derivative represented by formula (II) is added thereto. By adding and stirring, the compound (I) of the present invention can be obtained by rapidly reacting. If the reaction is difficult to proceed, the reaction can be facilitated by adding a small amount of a suitable base such as triethylamine, triethylenediamine, pyridine, sodium methoxide, sodium hydride, potassium carbonate, etc. Reaction formula 2 [In the formula, Q, G, L and X have the same meanings as above. Y represents an alkyl group having 1 to 6 carbon atoms or a phenyl group. ] That is, sulfamide sulfonamide derivative (IV)
chloroformic acid (
Compound (V) is obtained by reacting with thio)ester or carbonic acid (thio)ester. Compound (I) of the present invention can then be obtained by heating compound (I[) in a solvent such as toluene. (1; X=O) [In the formula, Q, G, L and Y have the same meanings as above. ] The reaction between sulfamides (VI) and phenyl N-chlorosulfonyl carbamate (■, Y = phenyl group) or alkyl N-chlorosulfonyl carbamate (■; Y = lower alkyl group) produces sulfamides (VI).
This is carried out using the carbamate derivative (■) in an amount of 0.5 to 3.0 moles per mole. Preferably, the amount ranges from 0.9 to 1.2 molar. The reaction temperature can be arbitrarily selected from the range of -50°C to 100°C, but is preferably in the range of -20°C to 30°C. This reaction is carried out using various bases. The amount of base is 0.5 to 4 per mole of sulfamide (VI).
．． 0 molar amount is used. Suitable bases include, for example, metal hydrides such as sodium hydride, metal alkoxides such as sodium ethoxide, alkyl metals such as n-butyllithium, triethylamine, pyridine, 1°8-diazabicyclo(5,
Organic bases such as 4,0)-7-undecene (DBU) and inorganic bases such as potassium hydroxide and sodium hydroxide are used. Particularly preferred is the use of metal hydrides. Suitable solvents for this reaction include solvents that are inert to this reaction,
For example, aromatic hydrocarbons such as benzene, toluene, and xylene, halogenated hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride, ethers such as ethyl ether, isopropyl ether, dioxane, and tetrahydrofuran, and nitriles such as acetonitrile and propionitrile. ,
Petroleum industry - hydrocarbons such as chill, petroleum benzene, hexane, etc.
These include ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, and amides such as dimethylformamide dimethylacetamide and hexamethylphosphoric triamide. These solvents may be used alone or in combination. Particularly preferred is the use of ethers or amides. Next, phenyl N-sulfamide sulfonyl carbamate (V; X=0.Y=phenyl group) or alkyl N-sulfamide sulfonyl carbamate (V
; X=O, Y=lower alkyl group) and compound (II) in a solvent such as benzene or toluene to obtain the compound of the present invention (■; X=0). (I;
The compound of the present invention (I:X=
O) can be obtained. Reaction formula 5 [In the formula, Q, G and L have the same meanings as above. ] That is, amines (In), tetrahydrofuran,
It is reacted with chlorosulfonyl isocyanate in a solvent such as dimethoxyethane, acetonitrile, propionitrile, dimethylformamide, dichloromethane, dichloroethane, benzene, toluene, etc., followed by triethylamine, pyridine, sodium hydride, sodium methoxide, sodium ethoxide, The compound of the present invention (I
; X=O) can be obtained. Reaction Formula 6 % Formula % [In the formula, Q and G have the same meanings as above. ] That is, the sulfamide sulfonamide derivative (IV),
In a solvent such as acetone, acetonitrile, dioxane, an inorganic base such as potassium carbonate, or triethylamine,
In the presence of an organic base such as DBU, the compound of the present invention (I;
X2S. L=H) can be obtained. The raw material sulfamide sulfonyl iso(thio)cyanate derivative (I[) used in reaction formula 1 is obtained from the sulfamide sulfonamide derivative (IV) according to JP-A-58-14.
It can be synthesized by referring to the methods described in JP-A No. 8879, JP-A-59-31775, JP-A-55-13266, and the like. In addition, sulfamide sulfonyl isocyanate (II
; (VI) O(X) Δ [In the formula, Q has the same meaning as above. ] Sulfamide sulfonyl iso(thio)cyanate derivative (■), sulfamide sulfonamide derivative (■), phenyl N-sulfamide sulfonyl (■), which is an intermediate used in the present invention
Thio)carnocmate (V; Y-niphenyl group) and alkyl N-sulfamidesulfonyl (thio)carbamate) (V; Y-lower alkyl group) are also new compounds. The sulfamide sulfonamide derivative (IV) can be prepared using the following reaction formulas 8 and 9.
) can be synthesized. Reaction formula 8% formula %) () [wherein, Q has the same meaning as above. ] In the reaction formula, the tert-butyl group is removed using trifluoroacetic acid. The amount of trifluoroacetic acid can be arbitrarily selected from an equimolar amount to an excess amount. There is no problem in using trifluoroacetic acid as a solvent. The reaction temperature can be arbitrarily selected from the range of -50°C to 80°C. Preferably, the temperature is within the range of -20°C to 30°C. When using a solvent in this reaction, use a solvent that is inert to this reaction, such as benzene, toluene, aromatic hydrocarbons such as xylene, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, ethyl ether, isopropyl Ethers such as ether, dioxane and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, hydrocarbons such as petroleum ether, petroleum benzyl and hexane, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, dimethylformamide, Amides such as dimethylacetamide and hexamethylphosphoric triamide. These solvents may be used alone or in combination. Reaction Formula 9 (In the formula, Q has the same meaning as above.) In Reaction Formula 9, the reaction between t-butanol and chlorosulfonyl isocyanate is carried out by a method known per se, for example, JP-A-50
This can be carried out with reference to Japanese Patent No.-101323. In the reaction between sulfamides (VI) and tert-butylsulfamoyl chloride, 0 tert-butylsulfamoyl chloride is added per mole of sulfamides (VI).
．． It is carried out using 5 to 3.0 molar amounts. The amount is preferably in the range of 0.9 to 1.2 moles. The reaction temperature can be arbitrarily selected from the range of -50°C to 100°C, preferably from -20°C to 30°C. This reaction is carried out using various bases. The amount of base is 0.5 to 4.0 per mole of sulfamide (VI).
Molar amounts are used. Preferably, a range of 0.8 to 2.2 molar amounts is suitable. Suitable bases include, for example, metal hydrides such as sodium hydride, metal alkoxides such as sodium ethoxide, alkyl metals such as n-butyllithium, triethylamine, pyridine, 1.8-
Diazabicyclo(5,4,0)-7-undecene(D
Organic bases such as B U) and inorganic bases such as potassium hydroxide and sodium hydroxide are used. Particularly preferred is the use of metal hydrides. Suitable solvents for this reaction include solvents that are inert to this reaction,
For example, aromatic hydrocarbons such as benzene, toluene, and xylene, halogenated hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride, ethers such as ethyl ether, isopropyl ether, dioxane, and tetrahydrofuran, and nitriles such as acetonitrile and propionitrile. ,
Hydrocarbons such as petroleum ether, petroleum benzene, hexane, etc.
These include ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, and amides such as dimethylformamide, dimethylacetamide, and hexamethylphosphoric triamide. These solvents may be used alone or in combination. Particularly preferred is the case where ethers or amides are used. In reaction formula 3, phenyl N-chlorosulfonyl carbamate (■, Y=phenyl group) and alkyl N-
Chlorsulfonyl carbamate (■, Y = lower alkyl group) can be prepared by methods known per se, for example Chemische Berichte.
, vol. 96, p. 56 (1963). Sulfamides (
VI) is the Journal of the American Chemical Society.
erican Chemical 5ociety),
Volume 66, page 1242 (1944), U.S. Patent No. 2.826.594, Journal of Synthetic Organic Chemistry, Volume 27 (
No. 1θ), 980 pages (1969), U.S. Patent No. 2.624.729, Chemische Berichte, 1
Volume 11, page 1915 (1978), JP-A-1973-
No. 79894, Japanese Patent Application Laid-open No. 58-208289,
Indian Journal of Chemistry, Section B
emistry, 5ection B), Volume 21B,
941 (1982) etc. can be referred to for synthesis. Representative examples include N,N-dimethyl-No-methoxysulfamide, N-methyl-N-methoxy-N-ethylsulfamide, N-methyl-N-methoxy-No-methoxysulfamide, N,N- Dimethyl-No-trifluoromethylthiosulfamide, N-methyl-N-methoxy-N
-Trichloromethylthiosulfamide and 2-methoxy-1,2,5-thiadiazolidine-1,1-dioxide synthesis methods are described in Reaction Schemes 10 to 15. Reaction formula 10 Reaction formula 1 Reaction formula 12 Reaction formula 1 Reaction formula! Reaction formula 15 The synthesis flJ of the compound of the present invention is shown below)ffi fl+
However, the present invention 1 is not limited to these examples. Example 1 1-1: (N-dimethylsulfamoyl-N-methoxy-amino)sulfonyl)-3-(4, Synthesis of 6-cymethoxypyrimidin-2-yl) urea (compound Nα1) 55% sodium hydride 1.87 g (42.9 mmon
) containing 00ml of anhydrous THF, 2 ml of anhydrous THF
3.0 g (19.5 mmof) of N,N-dimethyl-N-methoxysulfamide dissolved in 0 J was added under water cooling, and the mixture was stirred for 10 minutes at the same temperature. Next, 1x phenyl N-chlorosulfonyl compound containing 4.83 g (20,5 mm+) of phenyl N-chlorosulfonyl
50 ml of THF solution was added dropwise, and the temperature was gradually raised to room temperature.
The reaction mixture was then stirred at room temperature for 1 hour. The reaction mixture was poured into 500 ml of ice water containing 5 g of 35% hydrochloric acid and extracted with diethyl ether. The diethyl ether layer was washed successively with water and saturated brine, and then anhydrous. After drying over magnesium sulfate, the solvent was distilled off under reduced pressure.Phenyl N-((N-dimethylsulfamoyl-Nmethoxy-amino)sulfonyl fluoride was obtained as an orange oil.
5.4 g of bamate was obtained. Next, 3 g (8,5 mmol) of the above compound and 0.93 g (6 mmol) 2-amino-4,6-cymethoxypyrimidine were added.
A mixture of 20 ml of anhydrous benzene was heated to reflux for 10 minutes. After cooling, the solvent was distilled off under reduced pressure, and the residue was washed with ether and collected by filtration to obtain the desired 1-((N-dimethylsulfamoyl-N-methoxy-amino)sulfonyl)-3-(4 , 6-Simethoxypyrimidin-2-yl) urea (1.0 g) was obtained. Melting point 166-167°C Example 2 1-((N-(N-methyl-N-methoxyaminosulfonyl)-N-ethyl-amino)sulfonyl-3-(4,
Synthesis of 6-shifted xybi-1-nomidin-2-yl) urea (compound Nα20) 55% sodium hydride 1.60 g (36,7 mmo
ff) containing 50 ml of anhydrous THF, 20 ml of anhydrous THF
2.8 g (16.7 mm off) of N-methyl-N-methoxy N-ethylsulfamide dissolved in 1 ml was added under water cooling, and the mixture was stirred for 10 minutes at the same temperature. Next, phenyl N-chlorosulfonyl force-nokume) 4
．． Free KT containing 13g (17,5mmoffi)
Add 30 ml of HF, gradually raise the temperature to room temperature,
The mixture was subsequently stirred at room temperature for 1 hour. The reaction mixture was added to TC7 containing 4 g of 35% hydrochloric acid.
and extracted with diethyl ether. The diethyl ether layer was washed successively with water and saturated brine, then dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. Phenyl N-((N-(N-
5.0 g of methyl-N-methoxyaminosulfonyl)-N-ethyl-amino)sulfonyl)carbamate were obtained. Next, 2.5 g of the above compound (6,8 mmol, 2-
Amino-4,6-dimethoxypyrimidine 0.74g
(4.8 mmof) and 50 ml of anhydrous benzene was heated to reflux for 10 minutes. After cooling, the solvent was distilled off under reduced pressure, and the residue was washed with ether and collected by filtration to obtain the desired 1-(
(N-(N-methyl-N-methoxyaminosulfonyl)
-N-ethyl-amino)sulfonyl)-3-(4,6-
1.2 g of cymethoxypyrimidin-2-yl)urea were obtained. Melting point 157-158°C Example 3 l-(2-methoxy-1,2,5-thiadiazolidine-
1,1-dioxide-5-sulfonyl)-3-(4,6
-Simethoxypyrimidin-2-yl) urea synthesis (compound Nα22) 60% sodium hydride 0.25 g (6,25 mm
15 m of anhydrous tetrahydrofuran (THF) containing
2-methoxy-1°2.5-thiadiazolidine-1,1-dioxide 0,4 dissolved in 5 mj of anhydrous THF.
3 g (2.83 mmof) was added under water cooling, and then stirred at room temperature for 14 hours under a nitrogen stream. Next, after cooling the system to 0°C, 10 mj' of an anhydrous THF solution containing 0.7 g (3 mmol) of phenyl N-chlorosulfonyl carbamate was added dropwise, and then the temperature was gradually raised to room temperature, and then the system was cooled at room temperature. Stirred for 1 hour. The reaction mixture was mixed with 100 ml of ice water containing 0.6 g of 35% hydrochloric acid.
and extracted with diethyl ether. The diethyl ether layer was washed successively with water and saturated brine, then dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. 0.7 g of the target phenyl N-(2-methoxy-1,2,5-thiadiazolidine-1,1-dioxide-5-sulfonyl)carbame) was obtained as a yellow viscous oil. Next, 0.7 g (2 mmof) of the above compound, 0.31 g (2 mmof) of 2-amino-4,6-simethoxypyrimidine
of), anhydrous benzene lO- was heated to reflux for 10 minutes. After cooling, the solvent was distilled off under reduced pressure, and the resulting residue was washed with diethyl ether to obtain the desired 1-(2-methoxy-1,2,5-thiadiazolidine-1,1-dioxide-5). 0.5 g of -sulfonyl)-3-(4,6-cymethoxypyrimidin-2-yl)urea was obtained. Melting point: 162-163°C The structural formula and physical property values of the compound synthesized using the same method as in the above example are shown below. (Compound Nα2) (Compound Nα3) (Compound Nα4) Melting point 1 48-1 50°C Melting point 1 50-1 51”C Melting point 1 54-1 55°C (Compound Nα5) (Compound Nα6) (Compound Nα7) Melting point 1 44 ~1 45°C Melting point 1 38~1 39°C Melting point 1 27~1 28°C (Compound Nα8) Melting point 1 47~1 48°C (Compound Nα9) Melting point 1 31~1 32°C (Compound Nα1 Melting point l 0~ l l 1°C (Compound Nα11) Melting point 1 27-1 28°C (Compound Nα1 Melting point 1 18-1 20°C (Compound Nα1 Melting point 1 65-1 66°C (Compound Nα14) Melting point 1 37-1 39°C (Compound Nα1 Melting point 1 40-1 41°C (Compound Nα1 Melting point 1 50-1 51”C (Compound Nα17) Melting point 1 42°C (Compound Na 1 Melting point 1 47-1 48°C (Compound NcL1 Melting point 1 7-1 8°C) (Compound Nα21) Melting point: 151-152°C (hereinafter referred to as blank space) Next, examples of compounds included in the present invention, including the compounds synthesized in the above examples, are shown in Table 26 from Table 2 below. However, the compounds of the present invention are not limited to these. However, the symbols in the table each have the following meanings: Me: methyl group, Bt, ethyl group, Pr-n: normal propyl group, Pr-1; Isopropyl group, Pr-c; cyclopropyl group, Bun-n; normal butyl group, Bu-
s: secondary butyl group, Bu-i: isobutyl group,
But-t: tertiary-butyl group, Pen-n: normal pentyl group, Ph: phenyl group, Gn is the above-mentioned G
It has the same meaning as Ga, Gb, and Gc below. Ga=Gl-013 (meaning any of G1 to G13). Gb=Gl-G6 (meaning anything from GI to 66). Gc=Gl-03 (meaning anything from GI to 63). G13 (Hereinafter, blank) Table R item t (Me HEt Me Me Me Et Me Pr-n Me Pr-+ Me Bun Me Ph Me ph-C) 12 Et Et Pr-n Pr-low (CH2) 4 - -(CH2)S- HMe HEt Me Me Me Me Et Me Pr-n Continued Ct Ct Ct Ct Ct Ct Ct Ct Pr-n Pr-Ro Pr-n Pr-n Pr-n Pr-n Pr-n Pr- n Pr-n Pr-n Pr-ro Pr-mouth Pr-n Pr-c Pr-c Pr-c Pr-c Me Pr-i Me Bun-n Me Ph Me PtrCII2 Et Et Pr-n Pr-n -( CH2). (CH2)i- HMe HEt Me Me Me Me Et Me Pr-n Me Pri Me Bun Me Ph Me Ph-CH2 Et Et Pr-n Pr-n (Ct(z)-1(CI(t)a- HMe HEt Me Me Me Et Table 1 (continued) Pr-c Pr-c Pr-c Pr-c Pr-c Pr-c Pr-c Pr-c Pr-c CH2=CH CH, -CH CH,=CH CH , -CH C1+2=CH C112・C)l C112・Cl Cl+2・CH Cl1.=CH CH,=CH CH,=CH CH,=CH CH,=CH CH,・CHCH. CHt・CHCII. CH2−CHCH2 i2 Im Me Pr-n Me Pr-i Me Bu-roMe Ph Me Ph-CH. Et Et Pr-n Pr-ro (Ctlz)* (CH=)a- HMe HEI Me Me Me Et Me Pr-n Me Pr -i Me Bun Me Ph Me PtrCH□ Et Et Pr-n Pr-n (CH2)4- -(CH2)S- HMe HEt Me Me Table 1 (Continued) CI(,=CHCH. (t CH,=CHC)l.CH,・CHCH.C)I=CHCH.CH=CHCH.CH=CHC1(.CI=CHCH.CI=C)ICL CH=Cl1CH.HCCICH.HemiCCH.HC= CCH.oc=ccut)IC=CCHtHemiCC)I. HC=CCH* 1 (CmiCCH. HC-CCH. HC=CCH. HC=CCH. HC:CCH. IC:CCH. eOCHt MeOC) It Rth I3 Me Et Me Pr-n Me Pr-i Me Bu- n Me Ph Me PtrCHt EI Et Pr-n Pr-n -(CH2)4- 1(CH,)I- HMe HEt Me Me Me Et Me Pr-n Me Pr-i Me Bu-n Me Ph Me PtrCl(z Et Et Pr-n Pr-n -(CHri4- -(CH,)I- HMe HEt No.! Continued MeOCtl2 MeOCH2 MeOCH2 MeOCH2 MeOCtl. eOCHz eOCL MeOCH2 eOCHz MeOCH2 eOCHz P h Ph Ph Ph Ph Ph Ph Ph Ph Ph R1i! R ■ こ Me Me Me Et Me Pr-n Me Pr-i Me Bun Me Ph Me Ph-C112 Et Et Pr-n Pr-n -(C112)4- (CH2)6- HMe H81 Me Me Me Et Me Pr-n Me Pr-i Me Bun-n Me Ph Me PtrCHz Ph-CHt ■ Me Table 1 (continued) Ph-CHt Ph-CHt Ph-CHt PtrCHt Ph-Cut Ph-CI(t Ph-Cut Ph- CHt Ph-CHt Ph-CI(* Ph-CHt Ph-C)It Pr- Pr- Pr- Pr- Pr- Pr- Pr-i Bu-n Bun-n Bun-n Bun-n Bun-n Bun-n RI! HEt Me Me Me Et Me Pr-n Me Pr-i Me Bun Me Ph Me PtrCL Et Et Pr-n Pr-n -(cut)n- -(CHt)i- Me Me Me Me Bt Me Ph Me Ph-CHt ftt Bt -(CHri4- -(CL)l- Me Me Me Et Me Ph Me Ph-CHt Et Et -(Cut)4- ContinuedBu-n Bu-s Bu-s Bu-s Bu -s Bu-s Bus-s Bu-s Bu- Bu- Bu Bu Bu- Bu- Bu- But-t But-t But-t But-t But-t But-ten en-n en-n en -n -(CHt)-- Me Me Me Et Me Ph Me Ph-Cl1t EI Et -(CH2), - -(CH2)6- Me Me Me IEt Me Ph Me Ph-CHt Et Et -(C1ft), - -(C)1. ), - Me Me Me Et Me Ph Me Ph-C11t IEt Et (CL)4- -(CH2)I- Me Me Me Et Me Ph Cl-12 Et Et (CH2)4- (CH2)6- Me Me 口Me h-cH2 0, r r r r r r r -(CI□), - Me Me Me Et Me Ph Me PtrCHz Et Et -( CF(2)4- (CH2)I- Table continuation I2 R1+ CF CF CF 0 catty r r r r 〇- 〇- 〇- 〇- Me Me Me Me Et Me Ph Me Ph-CH2 Et Et (CH2), - - (CL), - Me Me Me Et Me Ph Me PtrCH2 Et Et (CH2), - (CHz) i- Me Me Me Me Et Me Ph \ To Levi ◇ To ◇ To ◇ To ◇ To ◇ To Me Ph-CH. Et Et -(CH2)4- -(CF(2)s- Me Me Me Et Me Ph Me PtrC) (z Bt Et ( CHt)4- -(CHt)*- Me Me Me Et Me Ph Me Ph-CI(2 Et Et -(CHI)4- Table continuation I2 ◇To O/″ O″″ A A A A A A ○ To ○ ○ to ○ to ○ to O to Et (CH2)4- -(CH,), - Me Me Me t Table 1 (continued) R″ Me=C=CH Me*C=C11 Me2C=CH Me, C=CH Me*C=CH Me2C= CI( MetC=CH MeCH=CHCH. Mech = Chcht Mec) I = Chcht MECL (= Chch * Mech = CICHT MECH = CHCI (! Mech = C) Ich * Ch, = C) (CH, CHT ME ME ET ME PH ME PLRCHT EL 8L - (CH , - -(cut)s- Me Me Me Et Me Ph Me Ph-CHI Et Et (CHI)4- -(CIri, - Me Me R1+ CH,= CIC112CII CH= ” CHCH2CH2 CH,= CIICIIICH. CI( , = CIICH,CH2 CH□= CIICI(2CH. CH2= CHCH,CI2 Me Et Me Ph Me PtrCf(t EI El - (CIri4- (C1lz)s- Table 1 (continued) R1+ 1t R'1 MeC =CCHt MeCmiCCH* MeC=CC)It MeC=CC1(t MeC=CCHt MeC:CCH* MeC=CCHt Me Me Me Et Me Ph Me Ph-CHt Et Et -(C1,), - -(CIriI - Table 1 (continued) R1+ I1CoMeOCHtCI(t MeOCIl, CL MeOCl(tcH* MeOCHtCHt MeOCHtCHt MeOC) ItCH* MeOCHtCHt EtOCl(tcH. EtOCLC) It EtOClltCHt EtO ClltCH. EtOCHtCH. EtOCl(*CI(t EtOCH, CH. MeOCMe .MeOCMe t MeOCMe ! MeOCMet MeOCMet MeOCMet MeOCMet Me Me Me Me Et Me Ph Me PtrC)It 11:t Et -(CHI), - (CH2)i- Me Me Me Me Et Me Ph M e Ph-C11t EI Et -(CL) 4- (CHri I- Me Me Me Et Me Ph Me PlrCHt Et Et (CHt)4- (CH2)l- Table 1 (continued) R1+ i EtO(CH2)4 Eta-(CI□)4 EtO(CH2 )4-EtO(CH2)4Eto-(CH2)4Eto-(CH2). EtO(CH2)4 eSCHt MeSC)lz eSCHt eSGHz Me Me Me Et Me Ph Me PtrCI(2 Et Et -(CHz)4- -(CH2)a- Me Me Me Et Me Ph Me PtrCI2 Table 1 (continued) eSCH2 MeSC112 MeSCH□ MeSC112CII2 MeSCI12CH2 MeSCH2CII2 MeSC112C112 MeSCH2CH2 MeSCH2CHz MeSCf(2CH2 FCF(2C1(2 FCH, CH. FCH, CI. F CH2CI2 FCHfC) 12 PCI (2CH. FCH, CII. CICH, CH2 IcI!2cH2 CHCH2CH2 CI CHzCHz CI CH2C) 12 CI CI(gcH2 CHCH2CL rCLCL l3 Et El -(C1(2), - (CH2)6 Me Me Me Et Me Ph Me PtrCII2 Et Et (CH2)4- 1(CH2). Me Me Me Me Me Et - (CH2) 4 (CH,), - Me Me Me Et Me Ph Me PtrCHz Et Et (CH2)4- (CH2)6- Me Me Table 1 (Continued) z BrCH2C1-1t CI CHtCHtCHt C4CHzCHzCHz CIICH2CH,CI. CI CH2Cl, CH. CI7 CH2CH2Ct(I CI C)12CH,CHI Ci CIl, CH, CH. Ct: -(Cut- C1-(CI(ri4- C1-(C L) 4-CI -(CH2)4 C1-(C:H2)4- C1(CHI)4 C1(CHI)4- R-eye Me Et Me Ph Me PtrCI2 Et Et -(CH2),--(CH2)i- Me Me Me Et Me Ph Me ph-cL Et Et -(CI(2),- (CH2)l- Me Me Me Et Me Ph Me Ph-CHt Et Et (C)12)4- (CL)s- Table Continued Rth Rth NCCII NCCH□ NCCH. NCCH2 NCCH. NCCH. NCCHt NCCII, CH2 NCCI (2C) I2 NCCH, CI. NCC)1. CH. NCCH2CH2 NCCI(,CH e Me Et Me Ph Me Ph-CHz Et Et (CI(2)4- -(cli- Me Me Me Et Me Ph Table 1 (continued) R1+ NCCH, CH2Cl. NCCll2CLCL NCCH, CH, CH. NCCLCLCL MeOtCCHt Me02CCHz MeLCC) (t MeOtCC L Me(ltccHt MeO, CCHt Me02CCH * EtOtCCHt EtOtCCHt EtOtCCHt EtOtCCHt EtOtCCl(. EtOtCCHt EtO, CCH. R1! R'2 Me PtrCHt Et Et -(CH2)4- -(CH,)s- Me Me Me Me Et Me Ph Me Ph-CI(t Et Et ( CHZ) 4- (CHZ) S -ME ME ET ME PH ME PH -C) IT ET EL (CH Rikari 4- (CH Riri I -Table 1 (continued) MEOZCCME * MeotCCME * MEOTCCMET MEO, CCME * MEOI * MEOI * MEOI * CCMET No. Me Me Ph Me PtrCHt Et Et -(CHt)a- -(CHt )s- MeO,CCH,CI(.MeOtCCHtCHt Table 1 (continued) MeOtCCHtCHt MeOtCCH2CIIt MeOtCCHtCHt MeOzCC)l*cHt MeO,CCH,C)I. EtO*CCH2CIIt EtOyCCl( *CHt EtO*CCH*C1(t EtOtCCHzCHt EtOtCCHtCI( tEtOxCCl (tcH. EtOtCCHtCHt MeOtCCHzCH, CHt MeO, CCHtCH*CH* MeOtCCHtC)ltcH* MeOtCCHtCHtCHt MeOtCCHtCHtCHt MeO, CCHtCH, CHt MeOtCCHtCHtCHt E tOtCCHtCHzCHz EtOtCCHzCHtCHt εtO*ccH*cHtcH* EtOtCCHzCHtCH* EtOtCCHzCHtCH* EtO*CC)ItCHtCH* R'! 1? 1! Me Ph Me Ph-Cl1゜Et Et -(CI(2)4- -(CHt)i- Me Me Me Et Me Ph Me PtrCHt EI El -(CL)4- - (CHt)s- Me Me Me Et Me Ph Me Ph-CH. MeCOCH2CMe2 MeCOCH2CMe2 MeCOCH2CMe x MeCOCH2CMe. MeCOCH2CMet - (CH2)S Me Me Me Et Me Ph Me ph-CH2 Et Et - (CH2), - - (CHz)s- = CHCH. BrC112C1l"" CHCH2 BrCH2CH" CHCH. BrCHzCH= CHCH. BrCH,CH"CHC)l. )4--(CL)i - CH2 MeO,CCH” CHCI(t MeO,CCH= CHCH. MeOtCCH= CHCH− MeO,CCH” CHCH. Table I (continued) Rth MeLCCl(= CIICH2 MeOzCCH=CHCHt Men2CCH= CHCI(. MeJCHtCHt Me, NCH, CH2 MelNCHtCH2 Me, NCHtCHz MeJCflzC) (z Me, NCH, CH. MeJC) ltcHx MetNCOCl (i Me, NCOCH. MetNCOCHx Me, NCOCHt MezNCOCH2 Me2N COCH. MetNCOC) (2 R11+ Et Et (CHz)4- -(CH2)6- Me Me Me Et Me Ph Me PtrCl(2 Et Et (CH2)4- -(CH□). Me Me Me Et Me Ph Me Pt'rCH2 Et Et -(CHz)*- (CH2)s- Atn [Tocl(t #CH! Me Me Me la a Continued) C←CH. $c) I2 C←CH. $c) (. $cH. Me ph Me PtrCH2 Et Et (CH2) 4- (CH7) 6- 1st table continuation R1! 1s n 1st nth continuation R1+ RI! n th continuation n th! continuation R1'' p+3 n th continuation R1+ R1! n th continuation R+t n n th continuation R at n th continuation R1+ R'! n e h a Table Continuation n (hereinafter, margin) 1st table continuation R1! R'kon. (hereinafter, margin) 1st table continuation R1+ R1! n 1st table continuation R item n 1st table (continued) R item 1s eCO eCO eCO eCO eCO eCO eCO eCO tCO tCO tCO tCO Btc. tCO tCO esCCO esCCO esCCO esCCO esCCO esCCO esCC0 Me Me Me Me Et Me Ph Me Ph-CHI Et Bt (CHI)4- -(cls- M e Me Me Et Me Ph Me PtrCt(* Bt Et − (CHt)4- (CI(t)i- Me Me Me Bt Me Ph Me PlrCHz Et Et (CHs)4- (CHri I- Table 1 (continued) Rth Cf, CI(CO Cz, CHCO C1ICHCO C1 , CHCO CA7 , CHCO Cf , CHCO CA) , CI(CO MeO*C MeO*C eOtC MeO*C MeO,C eOxC MeO*C tOIC tOtC tOtC tOtC tOzC EtO*C EtO*C C C C C R1 Ri Me Me Me Et Me Ph Me PtrCHz Et Et -(CL)*- (C)It)s- Me Me Me Et Me Ph Me Ph-CHt Et Et -(CIri4- -(cut)s- Me Me Me Et Me Ph Me PtrCHt Et El (CHI)4- (CHs)s- Me Me Me Et Me Ph Me Ph-CHI Table 1 (continued) C C C etNCO Me*NCO Me*NCO etNCO etNCO etNCO Me*NC0 R1! R1! ll! t Et (CHI)4- -(cut)i- Me Me Me Et Me Ph Me Ph-Cut Et Et (CHt)n- (CHI)i- Table (continued) p+2 n Table (continued) Table ( (continued) Table (continued) R1 con Table (continued) R1+ RI! rx n Table (continued) RI! n h e t r-n r-i r-c Table (continued) R1! Table 1 (Continued) 1? lt n Table (Continued) 6th Part (Continued) (Pr-c) CL u-n u-s u-t MeOCH, CH. EtSCHtCL ICH. Part (continued) R1+ h e Et Pr-n Pr-i u-n u-s u-t CL・CHCH. CH Mi CCH. MeOCH2EtSCH. MeSC) (tcHt EtSCH, CHt EI Gb Et Ga Et Gb Table (continued) R1+ R1 Rin Table (continued) RI+ 1?lff n Table (continued) I2 n Table (continued) RI! n (Hereafter, Margin) Table It Me Me Me Et Et Me -(CI(t), - Cl2=HCH(I Me CHtC=CHMe Ph Me PH-CHt Me Me Me Me Me Et Et Me (CHz)i- CH, C11=C11 , Me CH2C=CHMe Ph Me PH-CHt Me Me Me Me Et Et Me (CHt)s- Table 3 (Continued) r-n r-n r-n r-n r r r r P"P" r r r-cr r-c r-c r-c r-c r-c r-c r-c Shin Helle Bihe〉ha〉ha at C)12cH= CH2Me C)+2c=cHMe Ph Me PH-CHt Me 416 Me Me Et Ei Me (CH2)-- CH2CH= CH, Me CHzC=CHMe Ph Me PH-C)It Me Me Me Me Et Et Me (Ctlz)s- C)lzcl(=CH2Me CHzC=CHMe Ph Me P)I − CO, Me Me Me Me Et Et Me -(CHt)s- 8th R1!〉C〉A〉To〉CH1CH= CH2 CH2C: CI( Ph PH-CH. CFI, = CHCt(. CH2= CICI (- CHz = CHC) (t Me Ga Et Ga Me Gb CH, = CHC1 (2 C) 12 = CHCHt CH2 = CHC) (. CH, = CHCH. Cl2 = CHCH. HCCICH. uc = ccL HC =CCHt oc=ccot HC=CCH. HC=CCHt HCECC)It HC=CCH. eOCHt MeOCl(t eOCHt MeOCH* eOCHz eOCHt eOCHt eOCHt MeOCHtCHt MeOCHtCHz M eOCHtCHt MeOCHtCHt (CL)I CI(2CH=CH2 C1(, CECH Ph P) l-CH. Me Me Et (C)12) CH, CH=CH. CH2CECH Ph PH-C12 Me Me Et (CI(2)S- CH2CH= CH2 CH, C=CH Ph PH-CHt Me Me Et (CH2)!- MeOC) I 2 CH2 MeOC1'ltCL MeOCIl, CH. MeOCLC II. MeSClt MeSCl(*MeSCl(*MeSCllt MeSCl(*MeSCl(t eSCHt MeSCl(. MeSCHtCllx MeSCl(tcHt MeSC)ItCHt MeSCHsCHt MeSCII*C1lt MeSCHt CHt MeSCH-CHt MC11t, CHt FC) 1. CHI FC) IIC) l! FC) I , CH2 FC)1. CIl. FCH, CHI CLCH1 CH2CH=CH2 CH, C=CH Ph PH-C11. Me Me Et (CHz)s- C)l,tcH= CHt CH,C=c. Ph PH-CH. Me Me Et (CL)s- CH, CH=CH. C)1. c=ctt Ph PH-CH. Me Me Et -(CHI)-- CH, CH= CL Me CIbC=CHMe Continuation 1?11 FCH, CI. FCH,CI(. CA' CHtCHt CfCHICHt CICHICHI CI CHtCHt CfCHICHt CHCH2CHt CfCH,CIl. CfCHICL BrCHICHt BrCHtCl(* BrCHtCl(* BrC1(tcH. BrCHtC)lx BrCHtC)It BrCH,G11t BrCIltCH* NCCH. NCCI(t NCCII NCCII NCCII NCCII NCCH. 1t im (CHt)s- CH,CH=CH. CH,C=CH Ph PH-CH. Me Me (CHI)s- C1,CH= CI. C1,C=CH Ph PH-CH. Me Me Et (CHt)s- CH=CH=CHt Me CIbC=C)I Me Ph Me Table 3 (continued) NCCII. NCCIIICIl. NCC112CIlI NCCII, CIl. NCCH2CII! NCCl1.CHI NCC0zCHz NCC 0zCHz NCCH! C1l t MeOtCCHz MeOtCCllx MeOtCCHz MeOICCHt MeO, CCII. MeOtCCllx MeOtCCHz MeO*CCH. R1! t Me eMe Me Et Et Me (CL)s- CIl,CH= C1,Me clltc=cHMe Ph Me PH-Cllt Me EtO,CCH -(CHI)s- Table 3 (continued) I3 Ph Ph Ph Ph Ph Ph Ph Ph Ph Ph PtrCllt Ph -CHI Ph-CHI Ph-CHI Ph-CHI Ph-Cl1* Ph-Cl. Me Me Me Et Et Me ”'-(CHI)s- CH=CH=CII Me CLCECI(Me Ph Me PH-CHI Me 1st expression? +3 n Continued←C1(.GtocH2 ←CH.CH2 Day CI. $C)I a to cH. ←CH. Q ~ ■ To 10- 0 Me Me Me Et Et Me (CI C1, Me 6th Q~ Cl2C3CH h Me Me c b Drunk〇〇〇〇Me Me Et (CH=)s- Me Me a a b b 10~ S'5)- cozc= cH h Pt(-CHz Me Me Me Me Me Me c b c a Atn S'S) - Old Me b S) S) S) OR, CH=CH□ CHmC=CI+ h Me Me Me b c b (Hereinafter, the margin) Table 1m R1$ HMe HEt Me Me Me Et Me Pr-n Me Pr-i Me Bun Me Ph Me Ph-CHt Et Et Pr-n Pr -n (CIri4- (CHt)s- HMe HEt Me Me Me Et Me Pr-n Continued Bt Bt Bt Bt Bt Bt Bt Bt Pr-n Pr-n Pr-n Pr-n Pr-n Pr-n Pr-n Pr-n Pr-n Pr-n Pr-n Pr-n Pr-n CF. CF3 CF. CF. Me Pr-i Me Bun-n Me Ph Me Ph-CHt Et Et Pr-n Pr-n -(CI(1)4- (CI(t)s- HMe HEt Me Me Me Et Me Pr-n Me Pr-i Me Bun-n Me Ph Me Ph-CHt Et Bt Pr-n Pr-n (CHt) 4- -(CHt)i- HMe HEt Me Me Me Me Et Table 4 (continued) CF. CP. CF. CF. CF3 Fs CF. CF. CF. CCI!3 CCz* CCz. CCI!. CCz. CC1* Czs CCz* CCz* Czs Cfs Cf5 CCr. etNCO etNCO eJC0 R Me Pr-n Me Pr-i Me Bun Me Ph Me Ph-CHt Et Et Pr-n Pr-n -(CHri4- (CHt)s- HMe HEt Me Me Me Et Me Pr -n Me Pr-i Me Bu-n Me Ph Me PtrCHt Et Bt Pr-n Pr-n -(CHI)4- (CHRII- HMe HBt Me Me Table 4 (continued) eJCO etNCO ezNCO e2NCO ezNCO Me, NCO eJCO eJCO ezNCO etNCO Ph Ph Ph Ph Ph Ph Ph Ph Ph Me El Me Pr-n Me Pr-i Me Bun-n Me Ph Me Ph CH2 Et Et Pr-n Pr-n (CH2)4- (C)12) 6 - Me Me Me Et Me Ph Me Ph-CHt EI El -(CH2), - (CHa)s- Et (CI ri 4- a a a a b a 1st table continuation 1?I+ R1! n 1st table continuation i1m n 1st table continuation R1+ at II n 1st table continuation pH n 1st table continuation R item n (hereinafter referred to as margin) No. Table Is Me Me Me Bt -(CHt)s- CHtCH= CHt Me ClIC=CHMe Ph Me Me El -(CHt)s- Table continued R1! CF. Cf3 Cf3 C17I Cf3 CCI!. czs CC1* Ph Ph Ph Ph Ph P h PH PH Application -PH -CHT ME ME ME ET (CHZ) S -C1LTC = CHT ME C1 (TCECHME PH -CHT ME ME ME ME ET (Ch2) * ME C1ltC=CHMe Ph Me ph-cL Me Me Me Me Et -(CH2)s- CH, CH= CH. Me CHICECH Me Table R1! H n motion Et Br-n Br-i shame-n intuition Et flat Et Cl Br CF. side, F production tcf C1(*Br (continued) CH,l CH2CH2F CH2Cll2CI C112CH2Br CH2CH21 C)I(CHt,)CH2F CH(CHz)Cl12CII Cll(C11,)C12Br C1-1(C1,)CIl,r CI ( 20Me CH20Et C) (2CH20Me C)l, CH20Et C11(CH,)CI(20!14e CH(CH,)CH20Et CH20CII2CII=CH. CI(t001□c3cH C)I20CHF.0 group C et C84 goose o2SEt C (2sO2Me Open e t Fr-n Fr-i t-n Kant Guess E

[Cf Table (continued) B" ■ CF. 0(, F tcl side aBr 田, ■ (1) tc) ltF Q(2CH□C/ side, CH, Br CHtCH! I CH(CI(,)C1, F al(CH,)C11,Cf C1((CH-)CHtBr C1((CH,)CH,[ C1(J)Me 田、OE【口ItQ(を餉口It(&0Et CI((CHs)CI( zC&1e C) ((side,) CHt0Et CHloCH,CI(=CH. CHt(X&C=G( made!QC)FI C)1.0CF1 t FI t t t t t t t t t t E Fr-n Fr-n Fr-n Fr-n Fr-n Fr-n Fr-n Fr-n (continued) dtSMe CH,Set Open, SO2Me CHtSO2Et co2cp. H2cN o2Me 0tEt CO,Pr-n CH20CPs CI(tcOzEt O (, CO, Pr-n ω night OEt αFr-n Q(zcOMe (&C0Et 醗t ■ Threat l Gunch Fr-n Fr-n Fr-n Fr-n Fr-n Fr-n Fr-n Fr-n Fr- n Fr-n Fr-n Fr-n Fr-n Fr-n Fr-n Fr-n Fr-n Fr-n Fr-n Fr-n Fr-n Fr-n Fr-n Fr-n Fr-n Table (continued) t4 t CF. Made, F side tcf side tBr (1),! Open*CM/e CI(tOEt C)l!OCH,CI(=CH. CI(2α1.C=α 0(20CHPI CH20CPs G (,5- CH,5et CI(δ-intuition Q(tsOtBt CH, CF. ) R24 CI(zcOEt ■ Dynamic Et Me Et Me Et CF. Cl-1,F (1)2CI CH,Br Cl-121 CH2[1e CI-1,0Et CI(20CH,Cll=CH. C)(20CH2C= CH 0120CHF. C) 1.OcFI Cf(2SMe 12SEt (&SO2Me C) (2SO, Et r- r r- r r- r r- r- r- r- surface-n Bu-n ~-n -n Bu-n Bu-n Chest-n Bu-n ~-n ~-n Bu-n Bu-Roji-n Fu-n Table (continued) CH2CF. H2CN O2Me 02Et C112COJe Cl12CO2Et CO! ile OEt CH2COMe C112COEt Me ■ Me Me Cl2F C1l□CI C1(2Br CH21 CH20!i!e CH20CI1.Cl1=CI(. ) Bu- n Bu-n た-n Bun-n Bu-n ri-n ji-n ji-n CI(tcI(=C)(side*CI(-CL 田、CH=C)l.(21*C1( "side. Possible, CH=CH. 口12cl(-made. co, cH=made. cl12al=alt C1(,C)I-CH. C)Iz口+=CH. 口IzC1("CI(made, CI(-C)It 田, atoCHt 口1.C)l=(1).Open, CI=田. C11,CI(=CH(.口1.C)l=created. H2SMe C1(,SO ,Me cl(2C et al CH2(7) O2Me C)(,CO,Me Ile CH2COMe Me 平Et 醗Et CF. CI(2F H2Cz (&Br 田, I HJJe!0Et (&001.ctl=0(. 6th Table (continued) C11C1l=CI12 C11CI=CII2 CH2C1l=CH. C112CI=CH. C112C1l=CI( 012C1(=CIt. 012C)l=c) I. Cl1CIl=CH2 CII2CI(=CII. CIl□CII=CII. C112CI=CH. CH2Cmi openC1(2C30( CH20CII CLC=C)( CH2C:CH CHtCMicho CO, C=(1) CII2C=CH20CII□CECH Cl1□oc+(F2 CI(20CF. Ct(zS!ile H2SEt C112SO2Me CH2SO21Et CH2CF. H2a11 OJe O2Et C1 12CO2Me ■, CO□Et OMe 0Et CH20!i! e CH2CO[Ei ■ Me Et ■ Me I e Table 6 (continued) R21 CH, C Mi CH CH2C5 work CH2C Mirou C) I2C Mi CH Cl12C Mi side CH, C Mi CH CH2C Mi Cl Cl1.C Mi ■ C112C Mi side Cl2C5C) I CH2C Mi open cH2C Mi side CH2C5 creation CH2C Mi ■ CH2C3CH CH, CI (1) (&C=CH CH2C Mi CH CH, C Mi CH CH2C Mi CH mark, C Mi CH C1 (2C Mi CH CH, CmiCH CH2C3CH CH2CmiCH t FI CI (tF CH2C/ CH, Br CH, I CH*lle H20Et CJ120CH7C1l=C) It CH20C1l, CmiCH C) 120cllF. CH,0CFI CH2Ken e O(2SEt CH*SOzMe CHzSOtEt CH2CF. HICN CO□Me ωzEt CH2CO,Me CHtCO2Et αplaye OEt Table (Continued) R1+ R2″ n Mouth goes to〉to〉◇ To◇Me b b Part (Continued) R1' 2I CH=CHI CH=Saku. CH=CMet Q(=CMet CH2CH=CIille Rō, CH=CH Nori C1(, 口MI=田. C11zCH*C1(=C)lx Ajipi CH. CO, Ctonka't ) ,OEt 12SMe CI2 warme CHzolzSMe C112CH,SMe CH,CIl,F CH2Cl(2F Q(2CI12Cf CH2CI12Cf C1(tcH2Br C)I2CHtBr ■7ro1t(ltcII C)1.cH*cH2c 1 (G(J4C/ (Q( 2) 4Cf Part (continued) H2CN e1l□ (7) CH2C02Et C1l□CH2CN C1(□CH2CH2CN CH□C112CI2G11 CH2C02Et CHC112C I2G11CH2 CH2C02Et Part (:C02Me Me ■ CII2C112CO2Me CII2ClI2C112 CO2゜CH2C02Et ell□Cll2C02Et CH□CH2CH2CO2Me CI12C1l□CI12CCl12 CO2□ Cll2CII□CO□Et ell□CI□CH2C0□Et Uρ Me +C1C112CO Me Ph-Cl12 Ph-CH2 Cl12C1(=CHCH, Br 1(CH2CH=
CHC1(Jr H CH2Ctl=CIICOJe C112CH=口D2Me CHzCH,N11le. CHzC1lJ&Ie. Cl(2ωelectricet C112田dene. th OMe OMe oEt OE t COCJilc3 OCMez COCI ICl 2 COcIIClt CO□Me CO,Me 02Et 02Et CcNile2 ωden e2 R1' RN n Table (continued) R鵞4 C) 1.1 H52F CH2CO2Pr CI(2C1(2Br CI(, CI(, I CJI(C&)CI(2F Of(CI(,)CI(2(J' Cl1 (CHz)CH,Br C)((CHI3)al, I Q(201i1e H20Et Mouth J20!1le CH,C)120Et CH(Ols)CHzOMe Open(CHs)CHtOEt C11200(,CH=C)lI C1l,0CII2C =CI 口Iυf. CI(,OCF! MadetsMe CI(tsEt 田、SO2Me CHtSOzEt H2CFs H2a4 Table (continued) O2Me CO□Et CO2Pr-n (&CO2Me CI(2CO2Et CH2CO2Pr-n αNe OEt 0Pr-n Ct(2cO1ile CH2CH2t e t Br-n Br-i -n Intuition t e t Cl Table (continued) Br ■ Fs C11,F CH2Cl HtBr CI(, I CH2Cl, F CH2(&Ct; 口IzCH2Br 郎tcHzl CH(CH3)CI(,F CH(CI(,)CI12CI! 01(Ctb)C112Br Of(CHI)CI, I LOMe Ct(zOEt Q(,CH,0!1le C)I2CH,0Et CI((CHs)(&OMe CI((0(, )CI(,0Et CH,0CH2C)I=CH. C1(,OCH,C=CI CH,0CHF. CH, OCF. Pr-n Pr-n Pr-n Pr. Pr-n Pr-n Pr-n Continued H2SMc H2SEt CH2SO2Me C12CO2t H2CF3 H2CN O2Me 02Et (:02Pr-n CF(2cO2Me C12CO2Et C12CO2Et-n COMe OEt 0Pr-n CH2CO!1le CH2COEt e Et e Et e Pr-n Pr-n rn Pr-n Pr-n Pr-n Pr-n Pr-n Pr-n Pr-n Pr-n Pr-n Pr-n Pr-n Pr-n Pr -n Pr-n Pr-n Pr-n Pr-n Pr-n rn Pr-n Pr-n rn Succession Et CF. H2F Openzcl H2Br Hd CH2(le H20Et CH20CH2CH=CH2 CI20CH2C3CH CH20CI(F2 CH20C et H2SMe 12SEt CH2SO2Me CH2SO2Et CH2CF. I42CN O2Me (& Et CHt(&Me CH2C02Et CO!ile 0Et CH,COMe (continued) CH2COEt e Et e Et e Et CF. 112F H2CI H2Br CH21 CHzO!1le CI-1,0Et CH20CH2CH=CH2 CH20C82C:CH Cl12001F. CH,OCF. CI(2SMe C)12sEt CH2SO2Me CH2SOJt CF. CF. CF. CF. CF. CF. CF. CF C et CF. Czs Cl2 CCf. C12 Cl2 CCI!. CCI. CCI. C3- ccI!. Cl 2 CL C15 ccI!. CCI!. Continued Fil+4 CI (2CF. 2CO2Et COMe OEt CH20CI Cl12COEt CI e e e Fs CH,F CII2C1 CIl□Br CH21 ai, OMe CH20012CH=CH2 0120CI(2CmiCH C)(20CI(F. 郎20CF- CCI!* 碩mu cCi. CCV. Cfs Cl 5 CCI!2 CCI ! ωden e2 COt'＆1ez Candy e2 ω'JMe2 Tagu e2 ONMez ω1e2 j2 QN4e! Shout e2 (XNMe. ωden e. 田den e2 CONMe2 ωden e2 ωden e. 2Me CI ( C 0N11!et CC Kiri e2 C(P love2 CONMe2 CON!ile. COI'!1e2 C藷e2 COt1&Ie. Only e2 CONMe. 彊. α elbow 2 CcMAe. ■ Partial e. h h h Continued CI(20CH2C3Cl1 CH20CHF2 C120CF. CI( 2Skle H23Et CIIzSOzMe CI (asOtEt CIl, CF. Cl =CH CH, 0 open ZC = Rota !1le CH2COEt (blank below) R21 !1 e i Pr-ne e e CF. H2F C112CII HJr CI+21 CH201i1e C1120Et CH20CH2CH=CII. CII□0CI(2CmiCH CH2S)Je Ct(xsOJe (continued) H2S H2CN C0 □Me 02Et OMe OEt C12C02Me CH2CO,Et CH2COMe CH2COEt e Et Pr-ro I e e e CF. H2F CH2Cl 112Br Cl-121 CH20!1le C) 120Et Et Et Et E [ I Et I rn Pr. Pr-n Pr- n Pr-n Pr-n Pr-n Pr. Pr. Pr~n Pr-n Pr-n Pr-n Pr. Pr-n Pr-n Pr-1 Pr-i (continued) H2CN OMe OEt C112C02Me CH2CO□Et CH20!1le CH2COEt ■ e E【 Pr. ■ ■ e e e CF. H2F 1I2CI H2Br CH21 CH20file C1120Et e Pr Pr Pr Pr Pr Pr Pr Pr unun =CII.CH2CH =CH□ CH2Cll=Cl1゜Cll2C)l=clI2 CH□CII"CIIt C)12CII=CH2 Cl(2CIl=CH2 CH2CH=CH□ CH2Cll=CH2 CI12C=CH C12CE sign CH2Cl open C) (2C-:C H CH2Cyo CH (Continued) (Continued) R111 CH2C=CH C1I□CmiCa1 a+2c=a+ CH2C=CH u-s u-i 薗-t en-n r-c Ha. To ◇0(=CH(□ Q(scl (=C11Me C112C)I2CH=CH. HHHH HH) IH (continued) CI(2C= CMe ■ CH2O!1le CH2CIl□OMe CH2C02Et CMe, OMc (CH2)40Et H2SMe CH2C1(2SMe CH,0(2F Forcep 2C1(2CI CF(2cHJr Open, CH 2CH2C1 (CHz)4Cf CH,C111 CH2C1(,CN CH,CH2CH2CN CH2C02Et Part (continued) R1+ CH2C02Et +C02Et Me (JI2CHaCO2Me H (&CHzCO2Et H Cl1.C1(2CH2CO2Me HCl1ICH2
Cll
NIile, H OMe OEt COCMe 2 CoC1lCI! . 02Me 0zEt CH evening. He l Pr- Et OMe OEt C12COAe C112CO7Et CH2COMe CII2COEt e trn e e e e CP. CH, F C1, C47 HJr CH21 H20Me t I t t t t t t Pr-n rn Pr-n Pr-n rn rn rn Pr-n rn Pr-n rn Pr-n Pr-n Pr-n rn Pr- RoCF. Continued C1120Et H2CN OMe COεt CH2CO2Me CH2COJt C12COAle CII2COEt e t Pr-n e e e CF. l2F CI-12CI HJr CH21 H20Me H20Et R2+ ip? 2M n CP. CF3 Fi CF. C.F. C.F. CF3 CF. CCβ. CC1゜CCI! . CCβ3 CONMe2 CONMe 2 CONMe 2 ONMez CONMe2 CONMe2 CONMe2 CONMe 2 CONMe 2 h h h h 1st continuation R2? n (Hereafter, blank space) Table Me Me Me Me Me Me Me I Et Et Et I Et r-n r-n r-n r-n r-n Pr~n r-i r-i R1! Me Me Me Me Me Me Me Me Me Me Me Et -(CH2), - Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Et -(CIIJ4- Me Me Me Me Me Et C)12CH= Cl1I CI-12C-: CH Me Me Me Et CH2C11 = CI. CLC MiC) I Me Me Me Et CH, Cl=Cl1 CH2CEC11 Me Me Me l Table continuation r-i r-i r-i r-i r-c r-c r-c r-c r-c r -c CH, CH=CH. CHIC)l=cH* CH, CH=CH. CH*CH= CHt C1l, CH=CH. CHtCH=CH. oc=cco* uc=ccttt HC=CCH1 1(C:CCH! oc=CCHt HC=CCH. MeOCll. eOCL MeOCH* Rth Me Me Me Me Me Et -(CHri4- Me Me Me Me Me Me Me Me Me Me Et (CHz)4- Me Me Me Me Me Me Me Me Me Me Me Me Et (CHri4- Me Me Me Me Me Me Me Me Me Me Me Me Me Et -(CHt)4- Me Me Me Me Me Me Me Me Me otc mi C11 Me Me Me Et CH2C1(= C1l. CH,CmiCI Me Me Me Et CH,Cl=Cl1゜CI(,CmiCI Me Me Me Et CHIC)(=CH. cotcmiCI Me Me Me Et C)I , C) I= CH. th expression MeOCf(. MeOCIl. eOCL MeOC1l*CHt MeOCHtCHz MeOCl(, CH. MeOCl(tcH2 MeOcH, CI(2 MeOcH2C112 MeSC112 eSCHz eSCHz eSCHt MeSCII= eSCL MeSCH,CI(z MeSCl(,CI (t MeSCLCL MeSC) 1. Cll. MeSCHtCI (2 MeSCHzCHz FCHtCHt FCH,CH. e Et -(CHt,)4- Me Me Me Me Me Me Me Me Me Me Et - (CH2), - Me Me Me Me Me Me Me Me Me Me Me Et - (CHl) 4- Me Me Me Me Me Me Me Me Me Me CI (, CH Me Me Me Et CH2C1 l = CH. CH2Cmi CH Me Me Me Et CH2C)l= CIl. C) I, CmiCH Me Me Me Et CHICH= CI(t C82CmiC8 Table 10 (continued) FCH2CH2 FCH2CH2 CH=CH2CH2 CfCH2CH2 Cff1C112CII□ CfCH2CH2 Cj'CII□CI□ CIC!(, ClI2 CCH2 CCH2 NCCl+2 CCH2 CCH2 CCH2 NCCI(2C1-12 NCCH2CH2 NCCH2C112 NCCH2CH2 NCCl1.CH2 NCCH2CH2 EtO□CCH2 etO, ccH2 EtOzCCH□ EtO□CCH2 Et02CCH2 I2 13 L Me Et (CH2)4 Me Me 1i1e Me Me Me Me Me Me Me Et (C)+2)4 - Me Me Me Me Me Me Me Me Me Me Me Et (CIl2)4- Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Me Et Me Me Me Me Et CH2CH2 = C11t CH2CmiCH Me Me Me Et CH=CH2CH2 CH2CyoCH Me Me Me Et CH2CH= CIl 2 CH2CmiCH Me Me Me CH2CH=CH2 CH2CmiCH Me 0th table continued) R1+ EtO□CCI+2 I2 (C112). Me Ph Ph Ph Ph Ph Ph Ph Ph-CH□ Ph-CH2 Ph-CL Ph-CH2 Ph-CH2 Ph-CI. Me Me Me Me Me Me Me Me Me Me Et (C) (2) 4- Me Me Me Me Me Me Me Me Me Me -(CIl,)4 Me Et CH2CH=CH2 C1(2CEC11 Me Me Me Et CIl, CI = CIl 2 CH2CECH Me Me No. ■Continuation R1! n (Hereinafter, blank) No. 11 Me Me Me Me Me Me Me Me Me Et Et Et Et Et Pr-n Pr-n Pr-n Pr-n Pr-n Pr-ro Pr-i Pr-i 1?11' Me Me Me Me Me Me Me Me Me Me Et -(CH2), - Me Me Me Me Me Me Me Me Me Et -(CH2), - Me Me Me Me Me Me Me Me Me Me Me Et -(CH2), - Me Me Me Me Me Et C) 12CH=CH2 C112C MiCI-I Me Me Me Et CI(2CH=CH2 C1(2CmiCH Me Me Me Et CH=CH=CH. C) (2Cmi CH Me Me Me t Continuation r-i r-i r-i r-i r-c r-c r-c r-c r-c r-c CHt 2 = CHCH. Ctit= CHCH- CHz=CI(CHt CH,= CI(C)I. C1,= CHCH. CH2=CHCH. 11c:CCHt He=CCI(. HC=CCH* HC=CCH. HCCICI(! HCCICI(. h h h 81m Me Me Me Me Me Et -(C112)3 Me Me Me Me Me Me Me Me Me Me Me Et (CL)s- Me Me Me Me Me Me Me Me Me Me Me Et '-(CL)s- Me Me Me Me Me Me Me Me Me Me Me Et (C1,)!- Me Me Me Me Me Me CH, CH=CH. CH2C=CH Me Me Me Bt CH, CI (= CII CHzC=c. Me Me Me Bt CH, CH=CH. Ctl , C=CH Me Me Me Bt CH,CH= C)l. CH,C=CH Me Me Me Bt CHICH=CH! 2 h-CH2 Me Me Me Et (CH2)2- Me Me Me Me Me Me Me Me Me Me Me Me Et - (CH2:h- CH2C=cH Me Me Me Bt CH2CH= CH2 CH2C=CH Me Me Hereinafter, margin) 12th Table C1 Snow R eyes Me Me Me Me Me Me Me Me Me Me Bt (CHt) a- Me Me Me Me Me Me Me Me Me Me Me Et - (cut- Me Me Me Me Me Me Me Me Me Me Me Me Et (CHz) a- Me Me Me Me Me Bt CI (ICH=CL co*c=c. Me Me Me Bt C1, CH=CH. cotc2 CH Me Me Me Bt co*cu= cut C1,C=CH Me Me Me Bt 12 continuation) CCI! . CCI! . C.C.Z. CC1゜h h h h h h h C1 station Me Me Me Me Me Me Et (C) li 4 Me Me Me Me Me Me Me Me Me Me Me Et (C1,), - CH, CH= cot CHIC=CI1 Me Me Me CI CH, CH= C)II CO*Cmi CH Me e Table 13 Me Me Me Me Me Me Me Me Me Me Et (CH2)s Me Me Me Me Me Me Me Me Me Et (CHt, ), - Me Me Me Me Me Me Me Me Me Et -(CH,), - Me Me Me Me Me Et CH, Cl1=011°CI, C=CI(Me Me Me Et CH2C)l=CH. CH2C=CH Me Me Me Et C)IICH2C11°CH,C:CH Me Me Me Et] Continued CCi. CCI! . C.I. CCI! . h h h h h h 1ff Me Me Me Me Me Me Et -(CH2). Me Me Me Me Me Me Me Me Old-(C112)2 Cll2CI=C112 CH2CyoC1-I Me Me Me Et C)l 2C1(= CIl I CH2CCH2 C= CH Me Me Et I CHtCtl”CI(* CH2C1( = CI. CH2C=CH C) 1.c: CH Me Me E [ Et C1, CH=C) I2 C) 1. CH= CIl. CH2C=CH CH, CEC) I Me Me Et Et Continuation Pr- Mouth Pr-n Pr-n Pr-n Pr Pr Pr- Pr Pr Pr Pr P" Pr Pr Pr-c Pr-c Pr-c Pr-c Pr-c rc Pr-c Pr-c C112CIl=C1(. CH2CII=CI (. CI, CI = C) I. CH2C=CIl. CI, CIl = C1l. CH2Cl(=CH. CI, Cl-1= CIl. CH= C112 CH2CII=C)I. CH2C=CH Cl1.CmiCH Me Me Et I CH,CH=CH2 CHtCH""CHt CH,C-:CH CH,C=CI( Me Me Et Et CH,CH= CH. Continuation C112CIl=CII□ CIl, Cl1=CH2 C1l, CII=CII. Cl-12cmCl1 cutc=c. CIl, C=Cl1 cHtc=c. CH,C=Cl1 CH2CH2:Cl Cl1.C4i:CH CH2C :CI Ct(tOMe CH2CH2 HzOMe HJMe C)I20Me C)lJMe C1l, OMe CIl, OMe CH2CH2 H2SMe CIItSMe HtSMe CtltSMe CtltSMe R2 CH2CH= C) l 2 C H2C=CH C1(2C=CI( Me Met t CH, CH =CH. C) (,C)l=cH. C1,C=C)I CH,ccl Me Me εt t CH,CH=CH. C)I2CH=CH* C1(tc=C)I CH,C= CH Me Me t t CI, CH=C)I! cH2cH=cHt th expression Ra+ Ct(zsMe CIIzSMe CH2CH2P CIl, CIl, F C1(, CH2F Cl1.CH2F CH2C1(, F Ct12Ct(tF CHlCH,F C1l, CIl , F CH2CH=CH CHzCHtCf CH,CH2Cf C) (tcHtcl C1l, CH, Cl Cl1□CIl, CI CHtCHtCII CII□C)11cf ll2CN CH,CN C11,CN CI(,CN H2CN CH,C N H2CN tt ta CI(, C2CH CIl, CECII Me Met t CI (,CH2CH2°C)1. cH=cH. cotc=c. CH2C=CH (Me Met t C)1. Cll=C1l. CI(,CH=C)l. C11,C=I=CH C1(,C:C11 Me Met t CH2CH=CH(*C)I,CH=CH. Cl2CECH 1st expression Rz+ l12CN CH2CO,Me C1l, CO, Me Cll, CO2Me C11, CO2Me CHzCOtMe CHtCOtMe CHtCOtMe CH2CH2Me Ph Ph Ph Ph Ph Ph Ph Ph Ph Ph-CI. Ph-CHt Ph-cl(! ph-CH. ph-CHt Ph-CHt Ph-CH. Ph-CHt tta s CIl, C=CH Me Me E[ t CH, CI (=CH. C) 1. cH=c) I. CI (, C=C) I C) 1. cMiC) 1 Me Me t t CH2CH=CH. Cl2CH=CH. C11,C:CH CH,C=C)I Me Me t I CH2CH=CH. cutco=cot CH,C=CH cotc=c. OMe OMe OMe OMe OMe OMe OMe OMe OtMe Continuing Me Me t t CI, CII=CII. CH, Cl=Cl1゜Ct+*Cmi CH CH, CECH e CO□Me CO2Me O2Me O2Me CO, Me O2Mc CO7Me N N N N N N N N N CONMe2 CONMe2 CONMe2 CONMe2 CONMe2 ONMet CONMe. CONMe. u-n u-s Continue Me Et Et Cl2CECI□ CIl, Cl1=CH2 CH, CEC1l CH2Cmi CH Me Me E [I Cl2CECII. CI (, Cl=Cl1゜ct12c=ct+ Cl2CECII Me Me Et Et CH2CII=C112 CH□CH=C) 1.1 CH2CHCN CH,C-EC) (Me Me u-i u-t en-n > CIl CH2Cf (=CIIMe H Cl12C112CH=CII□H It HMe HMe Cl2CECII C112CII, OMe H C) I2CH20Et H p HMe H) 1Me (C112)<OEt CII2CII2SMe C112CIIJr CH2 CII2CH2CI! (CIl2)4C1 CI+2cH,cN C1I□CIl□CH2CN C11□C02Et HIIMe )It (HMe HHMe CII2C)I, CO, Me H CH2C11,CO,Et H Cl1. CIl, CI(, CO, Me HHMe HMe Hl(Me Et tt CH, CI(2Cl(2CO, Et D C112CH=CIICH-Br C1-1, cll=cllcO, Me C) 12cl12NMet CHtCONMet OEt OCMes CO CIICi'. Me Me t t CH2CH=CH2 CHzCt(=CHt co*c=c. cotc=c. Me Me I t CH2CI = CIl. CIl, CH=CH. CI, C=CH CH, C: CH Me Me t t CF CF. CF. CF. CCI!2 Cl5 CCf. Czs czs CCI!2 CZ3 CCI!I CONMe2 ONMet ONMet CONMe* CONMe2 CONMe. ONMet CONMe. h h h h h h Continued CH2C) I=C112 C02CH=CI. CH2C= CH Me Me t t CH, CH=CH2゜CH, Cl1=CII. CI(, C=CH CIIIC=CII Me Me t t CIl, CH=CH. CH=CH=CH. CH, C =CH CH,C=CH Me Me I t CH, CH=CH2゜Continued HMe H HHH II Me H CH, CIl = CIl I CH, CECH cntc2CH (Hereafter, blank space) R2+ R6R16 pt7 R1= L Me Me Me Me Me t I t I t r-n r-n r-n r-n r-n C)bcH=cl(* C1-1, CH=CH2 C1(, CH=CH. CHzCI=C1l* Cl1tC ) l=cHt Me t C02CH=CHt C) 1. C=CH Me Me El ・ CIICH=C) l. cutc=c. Me Me t CHaCl (=CH* CH,CmiC11 Me Me I CH,C) I=CI-1゜C) IIC2CH e Table 16 (continued) RI RI feeling C1I□CECI+ cotc=c. CIl, C2CH cutc=c. CIl, C=:C1+ h h h h h ri u -n u-s u-i u-t en-n r-c 〉 ■ ■ RI R2= 1 I1 Me CII=CI+. ■ Me CII2CH=CIIMe H CH2CH2C) I=CI(,H )I HHMe Hl( HMe CH2CHCMe C112CIl Cll 2 C1l 20Me CH2CIItOEt p HH, HHMe Gb II HHIt Me GbHl (
HHMeGb (C11□), OEt H2SMe CH2Cl, SMe C1l□CH2F CH2CH2CI CH2Cl, Br C) I2CH, CIl, Cf (CHt) 4C1' 112CN C112C112CN C112CIl, CIl, CN Cl12 CO2Me CCNC112CO 2 & CIItCO2Me C11, Cll, CO, Et CHtCI12CHtCOJe CIlyCIl *Cf1tCOJt Uρ Me h-CHt ■ No. C11, CII=CIICO2Me HCIIzC1
12NMe, H Cl1□CONMe, H HHIIMeGb HHHMeGb HHHMeGb OMe OEt OCMez COCIICi' to2Me 02Et CN ONMet I2L Me Et CIl, CH=CH. Cl2CEC1( Me Me CHfC=CH. cotc=cu Me Me Et CHzCl(=CH* CHICmiCH Me Me E[ CH, CI(=CH. CHf1C=:CH Me Continued R1# Me Et C) I2CH=CHt CH, C: CH Me (Hereafter, blank space) Table Me Me Me Me E [ Et Et Et r-n r-n r-n r-n r-i r-j r-i r-i r-c r-c r-c r-c Me Me Me Et -(CHI)4- -(CHz)s- Me Me Me Fit -(CHI)4- -(CHI)a- Me Me Me Et -(C1l,)4- - (CI□), - Me Me Me Et - (cut) 4- (CH2) 6- eMe Me E [ - (CHI) 4- ~ (CHz) i- th continuation CHz=CHCIIt CH, = C) IcII. C) (!=CHCH1 CH,=CHCH. HC=CCHI HC=CCH! HC=CCH. 1(C=CCH. Ph Ph Ph Ph Ph Ph-C)It Ph-C)It ph-c)l! Pb-CHI R1! I3 Kanki Me Et (CHt) i- - (CIri, - Me Me Me Et - (CIri 4- - (C1(t)i- Me IJe Me Et (CHI)4- -(CHI)i- Me Me Me Et -(C)11), - -(C1lt)i- (Hereafter, margin) R1 R1! n (Hereafter, margin) Table Me Me Me Met t t I r-n r-n r-n r-n r-i r-i r-i r-i r-c r-c r-c r-c Me Me -(CL)s- C) lxCH= CH, Me CH*C=C1l Me Me Me -(cl* CH,CH"C1,Me CHtCECHMe Me Me -(CHri, - CH,CI= CH,Me CHtCECHMe Me Me -(CHt)a- CH*CH=CHt Me CH*C=CHMe Me Me - (CI(,),-C)lICH=CI! Me CHIC=CHMe th expression R1+ CHt , = CHCH. CH,= ClCl. CH2= CHCH. C1l , = CHCH. HC2CCH. HC:CCHI HCCICI(t ) IC=CCH. Ph Ph Ph Ph Ph Ph-CI(. Ph-cot Ph-CHt Ph-CH2 R+t Me Me (CHt)s- CHICH=CII. Cl42CEC1( Me -(CI(2), - Ct( * C1(= C1(- CLC-:C1( Me-(CI(,),-CHzCH= Cl- Cl1.C:CH Me (Cllt)s- CH, CH=CH. cotc=ct+ (hereinafter, margin) Table R1'' Me Me Me Et - (CI ri, - (CI ri - - 11e Work Me Et (CHt) 4- (CI ri l - Me Me Me Et (CI'l ri 4- (CHl)s- Me Me Me Et -(CHt)4- -(CI=)s- Me Me Me Et -(CHt)4- -(cls)s- Continuation R1+ R1! n 10- Me Me Me -(CIri,- a b b (Hereafter, blank space) Table I3 Me Me (CHt)x- CH*CH= CHt Me C1bCE CI Me Me Me (CHt)*- CHlCl'1=CH* Me cHtc=ctt Me Me Me -(cut )s- CIbCH=CH*Me CH,C=CHMe Me Me-(CI(,). C When applied as a herbicide, a suitable carrier is generally used, such as a solid carrier such as clay, talc, bentonite, diatomaceous earth, or water, alcohol (methanol, ethanol, etc.), aromatic hydrocarbons (benzene, ethanol, etc.).
It can be applied in combination with a liquid carrier such as chlorinated hydrocarbons (toluene, xylene, etc.), ethers, ketones, esters (ethyl acetate, etc.), acid amides (dimethylformamide, etc.), and if desired, an emulsifier. , a dispersing agent, a suspending agent, a penetrating agent, a spreading agent, a stabilizer, etc. can be added, and it can be put to practical use in any desired dosage form such as a liquid, emulsion, wettable powder, powder, granule, or flowable. Next, examples of formulations of herbicides containing the compound of the present invention as an active ingredient will be shown, but the invention is not limited thereto. In addition, in the following formulation examples, [parts] means parts by weight. Formulation example 1 Wettable powder Compound of the present invention Nα1...
・－・・・－・－・20 parts Sieglite A ・・・・
・－・・・・・・・・・・・・・・・・・・ 76 copies (
Kaolin clay: Sieglite Kogyo ■Product name) Tsurupol 5039・・・・・・・・・・・・・・・・・・
-... 2 parts (nonionic surfactant, mixture of sex agent and anionic surfactant: Toho Chemical ■trade name) Carplex (anti-caking agent)... 2 parts (white carbon: Shiono (Product name from Gisei Pharmaceutical Co., Ltd.) The above was mixed and pulverized uniformly to make a wettable powder. Formulation example 2 Wettable powder Compound of the present invention Nα2...
・・・・・・－・・ Part 40 Sieglite A ・・・
・・・・・・・・・・・・・・・・・・・・・ 54 parts (Kaolin clay: Sieglite Kogyo ■Product name) Tsurupol 5039・・・・・・・・・・・・・・・・・・
-... 2 parts (Mixture of nonionic surfactant and anionic surfactant: Toho Chemical ■Product name) Carplex (anti-caking agent)... 4 parts (White carbon: Shionogi & Co., Ltd. (trade name) The above was mixed and pulverized uniformly to make a wettable powder. Formulation Example 3 Emulsion Compound of the Invention Na3 ・・・−・−・・・・・・・
・・・・・・－・ 5th part
・・・・・・・・・・・・・・・・・・・・・ 75
Dimethylformamide・・・・・・・・・・・・・・・
-・・・・・・15 part Tsurupol 2680・・・・・・
・・・・・・・・・・・・・・・・・・ 5 parts (mixture of nonionic surfactant and anionic surfactant: Toho Chemical ■trade name) Mix the above uniformly and make an emulsion. did. When used, the above emulsion was diluted 10 to 10.000 times and sprayed at an amount of active ingredient of 0.005 to 10 kg per hectare. Formulation Example 470 Able Compound of the Invention Nα4 ・・・・・・・・・・・・・・
・・・・・・ 25 parts Ageli Seal S-710・・・・
・・・・・・・・・・・・ 10 parts (nonionic surfactant: Kao brand name) Lunox 100OC・・・・・・
・・Song・・0.5 part (Anionic surfactant: Toho Chemical ■Product name) 1% Rhodobol water ・・・・・・・・・
...
・・・・・・・・・・・・・・・44.5 parts or more of the song was uniformly mixed to make a flowable agent. Formulation Example 570 Apple Compound of the Invention Nα20 ・・・・・・・・・・・・・・・
・・・・・・・・・・40 parts Ageliseal S-710...Songs・・10 parts (Nonionic surfactant: Kao brand name) Lunox 100Oc・・・・・・・・・・・・・・・・・・
...... 0.5 part (anionic surfactant: Toho Chemical ■trade name) 1% Rhodobol water ...
・・・・・・・・・・・・ 20 parts (thickener: Rota-Boulin product name) Water ・・・・・・
・・・・・・・・・・・・・・・－・・・・・・・・・
...29.5 parts or more were uniformly mixed to form a flowable agent. Formulation example 6 Granules Compound of the present invention Nα22・・・・・・・・・・・・・・・・・・
・・・・・・・ Part 1 Bentonite ・・・・
・・・－・・・・・・・・・－・・・－・55th part tarri ・・・・・・・・・・−・Bashing...
- After uniformly mixing and pulverizing 44 parts or more, a small amount of water was added and the mixture was stirred and kneaded, granulated using an extrusion granulator, and dried to form granules. Furthermore, the compound of the present invention may be applied in combination with other herbicides, various insecticides, fungicides, synergists, etc. when preparing or spraying, if necessary. Other types of herbicides mentioned above include, for example, Farm Chemicals Handbook.
There are compounds described in the 1989 edition of Handbook. For example, the compounds of the present invention include alachlor, acetochlor, metolachlor, brimisulfuron, nicosulfuron, atrazine, cyanazine, EPTC12,4-D,
butyrate, dicambabromoxynil, tridayfan, metsulfuron-methyl, thifensulfuron-methyl, triasulfuron, isobrothiuron, chlorotoluron, diflufenican, metabenzthiazuron, diclofop-methyl, dipenzocort, fenoxaprop-ethyl, Pentacine, trifluralin, fendimethalin and N-[(4,6-cymethoxypyrimidin-2-yl) as described in U.S. Pat. No. 4,668,277.
Herbicides such as aminocarbonyl 1-3-chloro-4-methoxycarbonyl-1-methylpyrazole-5-sulfonamide, 1,8-naphthoic anhydride and N,N-
Mixing with herbicide safeners such as diallyl-2,2-dichloroacetamide is possible. The compound of the present invention can be applied to control various weeds in agricultural and horticultural areas such as fields, paddy fields, and orchards, as well as in non-agricultural areas such as playgrounds, vacant lots, and railway edges, and the amount of the applied drug depends on the application situation. There are differences depending on the application time, application method, target grass species, cultivated crops, etc., but in general, the appropriate amount of active ingredient is about 0,005 to 100 kg per hectare. Next, the usefulness of the compounds of the present invention as herbicides will be specifically explained in the following test examples. However, the compound numbers in the test examples correspond to the aforementioned numbers. Test Example-1 Weeding Effect Test by Soil Treatment Sterilized diluvial soil was placed in a plastic box measuring 15 cm long, 22 cm wide, and 6 cm deep, and the fields were filled with wildflowers, crabgrass, cyperus, japonica, leafminer, ash, rice, corn, and wheat. , soybean and cotton mixed, about 1.5 cm
After covering the soil, the active ingredients were uniformly spread over the soil surface in a predetermined ratio. The chemical solution used for spraying was a wettable powder suitably prepared according to the formulation example described above, diluted with water, and sprayed over the entire surface with a small sprayer. Four weeks after spraying the chemical solution, the herbicidal effect on crops and various weeds was investigated according to the following criteria. The results are shown in Table 27. (Compound Nα corresponds to compound Nα described in the Examples.) Some of the compounds of the present invention have selectivity for certain crops. Judgment Criteria 5: Weed killing rate 90% or more (almost complete death) 4.
... Weed killing rate 70-90% 3... Weed killing rate 40-70% 2... Weed killing rate 20-40% 1... Weed killing rate 5-20% 0... Weed killing rate 5% or less (dove) However, the above-mentioned herbicidal rate was determined by measuring the weight of above-ground plants in the chemical-treated area and the weight of above-ground plants in the untreated area using the following formula. Test Example-2 Weeding effect test by foliage treatment Sterilized diluvial soil was placed in a plastic box measuring 15 cm long, 22 ann wide, and 6 cIn deep, and sterilized diluvial soil was placed in a plastic box measuring 15 cm long, 22 ann wide, and 6 cIn deep. Soybean, cotton, and beet seeds were sown in spots and covered with soil for about 1.5 am. When each plant reached the 2-3 leaf stage, the active ingredients were uniformly sprayed onto the stems and leaves at a predetermined ratio. The chemical solution used for spraying was the hydrating agent of the formulation example described above diluted with water and sprayed over the entire surface of the stems and leaves of various weeds using a small sprayer. Four weeks after spraying the chemical solution, the herbicidal effect on crops and various weeds was investigated according to the criteria of Test Example-1. The results are shown in Table 28. (Compound Nα corresponds to compound Nα described in Examples.) (Hereafter, blank space) Table 27 0.04 1 0.08 0.16 0, 04 2 0.08 0.16 0.04 3 0. 08 0.16 0.04 4 0.08 0.16 5 0.63 6 0.63 Table 27 (continued) 0.16 8 0.32 0.63 9 0.63 0.16 10 0.32 0 .63 11 0.63 0.16 13 0.32 0.63 14 0.63 15 0.63 Table 28 0.63 ■ Table 28 0.04 1 0.08 0.16 0.04 2 0. 08 0.16 0.04 3 0.08 0.16 0.04 4 0.08 0.16 5 0.63 6 0.63 434555431.555 Table 28 (continued) 0.16 0.63 4 2 5 5 5 5 2 1 0
5 5 50.04 5 2 5 3 5 5 4
4 0 4 4 40.16 (Hereinafter, blank) Next, the present inventors conducted research to increase the herbicidal effect of the compound of the present invention, and found that the compound of the present invention contains alachlor, acetochlor, and metolachlor. It was discovered that when either primisulfuron or nicosulfuron is combined, the herbicidal effects of each can be obtained not only additively but also synergistically without causing any phytotoxicity to crops. The synergistic herbicidal effect of herbicide mixtures can be explained as follows. That is, individual active compounds often exhibit drawbacks in their herbicidal activity, but in such cases, the herbicidal activity when two types of active compounds are combined is
When the activity of the two compounds is greater than the simple sum of their respective activities (expected activity), this is called synergism. The expected activity of a specific combination of two herbicides is
It can be calculated as follows. (Colby S, R, Calculation of synergistic and antagonistic responses of herbicide combinations rWeed 115, pp. 20-22, 19
67) l υ υ That is, if the actual inhibition rate is greater than the above calculation, it can be said that the combined activities exhibit synergism. Hereinafter, the present invention will be explained in more detail with reference to Examples, but the compounds, dosage amounts, dosage forms, etc. of the present invention are not limited to the Examples. In addition, "1 part" means all parts by weight. Formulation example 7 Wettable powder Compound of the present invention Nα3 ・・・・・・・・・・・・・・・−
・・・ 1O part brimisulfuron ・−・・−・−
・・・・・１O part Si-kulite PFP ・
−・・・・・・・・・−・・・・・・ 72 parts (kaolin clay: Gikrite Industries product name) Tsurupol 5039
・・・・・・・・・－・・・・・・ 2 parts (alkyl ether sulfate: Toho Chemical Industry ■Product name) Soybean oil −・・・・・・・・・・・・・・・・
・−・・ Part 2 Carplex #80 ・・・−・・
・・・－・・ Part 4 (White Carbon: Shionogi & Co., Ltd.■
Product name) The above was mixed and pulverized uniformly to make a wettable powder. Formulation example 8 Wettable powder Compound of the present invention Nα3 ・・・・・・・・・・・・・・・
−・・・−lO part Nicosulfuron −・−・・・・・・・
・・・・・・・・・・・・ 10 part zi-crite PPP
・・・・・・・・・－・・・・・・ 72 parts (Kaolin clay: Sieglite Industries ■Product name) Tsurupol 5
039 ・・・－・・・・・・・・・・・・-2 parts (alkyl ether sulfate: Toho Chemical Industry ■Product name) Soybean oil ・・・・・・・・・・・・・・・・・・
・・・・・・ Part 2 Carplex #80 ・・・・・・
... Four parts (white carbon: Shionogi & Co., Ltd. ■ trade name) or more were mixed and ground uniformly to prepare a wettable powder. Formulation Example 9 Suspending agent Compound of the present invention Nα3 ・・・・・・・・・・・・・・・
・・−・ Part 2 Alacroll −・−・・・−・
−・・・・・・・・・−・・・ 38 parts Tsurupon T-80・
・・・・・・・・・・・・・・・ 5 parts (Polyoxyethylene sorbitan monooleate: Toho Chemical Industry ■Product name) V-Gum ・・・・・・・・・・・・−
・・・・・・ 5 parts (magnesium aluminum silicate: Vanderbil company product name) Water ・・・・・・・・・・・・
...... 50 parts or more were mixed uniformly and ground using a sand mill or the like to obtain a suspension with a particle size of 5 microns or less. Formulation example 10 Suspending agent Compound of the present invention Nα3 ・・・・・・・・・・・・・・・・・・
・・・・・・ Part 2 acetochlor ・・・・・・
・・・・・・・・・－・・・ 38 parts Tsurupon T-80
−・−・・・・・・・・・・・・・ 5 parts (Polyoxyethylene sorbitan monooleate: Toho Chemical Industry ■Product name) V-Gum ・・−・〜・・・・・・・・・
-... 5 parts (magnesium aluminum silicate: Vanderbil company trade name) water -...
...-50 parts or more were mixed uniformly and ground using a sand mill or the like to obtain a suspension with a particle size of 5 microns or less. Formulation example 11 Granules Compound of the present invention Nα3 ・・・・・・・・・・・・・・・
・・・・・・ 5 parts metolachlor ・・・・・・・
・・・・・・・・・・・・ 75th part Aron A
・・・－・・・－・・・・・・・・・・・・ Part 7 (
Polycarboxylate Nitoa Gosei Kagaku ■Product name) Sun Extract C... - Song... 10 parts (lignin sulfonate: Choyo Kokusaku Pulp ■Product name) Newlex powder... ...-2 parts (DB
S-Na: NOF ■Product name) Zikrite PFP
・・・・・・・・・・・・・・・・・・ Add an appropriate amount of water to 1 part or more (kaolin clay: Sieglite Industries ■trade name), mix and grind to form a slurry, and dry this with a spray dryer. The mixture was made into granules while removing water. Formulation example 12 Granules Compound of the present invention Nα3 ・・・・・・・・・・・・・・・
・・・・・・ Part 5 Alacroll ・・・・・・・・・
−・・・・・・〜・・・・・・ 75th part Aron A
······························································································ 7 parts -・・・・・・・・・ 10
part (lignin sulfonate: Chongyang Kokusaku Valve - product name) Newrex Powder 2 parts (
DBS-Na: NOF ■Product name) Zeekrite PF
P ・・・・・・・・・・・・−・−・・・・ Add an appropriate amount of water to 1 part (kaolin clay: Sieglite Kogyo ■ trade name) or more, mix and grind to form a slurry, and spray this. It was made into granules while removing moisture with a dryer. Test Example 3 Weeding effect test by soil treatment Sterilized field soil was placed in a plastic box measuring 30 cm long, 30 cm wide, and 10 cm deep, and seeds of corn, foxtail grass, Japanese yam, and Japanese fir were sown in spots. 5
cm was covered with soil. The treatment was carried out on the day of sowing at a water rate of 51/a. The chemical solution used for spraying was appropriately adjusted according to the formulation example described above, diluted with water, and sprayed using a small sprayer. Three weeks after spraying the chemical solution, the above-ground fresh weight of each weed was measured, and the suppression rate (%) was calculated using the following formula. Table 29 shows the results of the herbicidal effect test for single agents. Table 30 shows the results of the herbicidal effect test of the mixture. (Compound Nα corresponds to the compound Nα described in the Examples.) Test Example-4 Weeding effect test by growth period treatment 30 cm long,
Fill a plastic box with a width of 30 cm and a depth of 10 cm with sterilized field soil, and sow seeds of corn, foxglove, Japanese ferret, and Japanese fir tree in spots.
cm was covered with soil. 51 on the 10th day of sowing! Spraying was carried out during the growing season with a water amount of /a. The chemical solution used for spraying was appropriately adjusted according to the formulation example described above, diluted with water, and sprayed using a small sprayer. Two weeks after spraying the chemical solution, the above-ground fresh weight of each weed was measured, and the suppression rate (%) was determined in the same manner as in Test Example-3. Table 31 shows the results of the herbicidal effect test for single agents. Table 32 shows the results of the herbicidal effect test of the mixture. (Compound Nα corresponds to the compound Nα described in the Examples.) (Hereinafter, blank space) Table 0, Ol Nα3 0.03 0.1 0.1 0.1 0.1 Table (Expected values are the Colby The values obtained from the formula are shown below. Table 0, Ol 0.1 0.01 0, Ol Nicosulfuron 0.03 0.1

Claims (3)

[Claims] (1) General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, Q is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ￥Q11￥￥Q12￥ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ￥Q13￥￥Q14￥ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ￥Q15￥￥Q21￥ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc.▼, ¥Q22¥¥Q23¥ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ¥Q24¥ Represents R^1^1, an alkyl group with 1 to 6 carbon atoms, and 3 to 7 carbon atoms. a cycloalkyl group having 3 to 7 carbon atoms, a cycloalkenyl group having 3 to 7 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with a cycloalkyl group having 3 to 7 carbon atoms,
an alkyl group having 1 to 6 carbon atoms substituted with a mono- or polyhalogenocycloalkyl group having 3 to 7 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, An alkyl group having 1 to 6 carbon atoms substituted with an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted by an alkylthio group having 1 to 6 carbon atoms, a carbon atom Numbers 1-6
an alkyl group having 1 to 6 carbon atoms substituted with a mono- or dialkylamino group, a mono- or polyhalogenoalkyl group having 1 to 6 carbon atoms, a mono- or polyhalogenoalkyl group having 2 to 6 carbon atoms;
6 mono- or polyhalogenoalkenyl group, an alkyl group having 1 to 6 carbon atoms substituted with a cyano group,
an alkyl group having 1 to 6 carbon atoms substituted with an alkoxycarbonyl group having 1 to 6 carbon atoms; an alkenyl group having 2 to 6 carbon atoms substituted by an alkoxycarbonyl group having 1 to 6 carbon atoms; A mono- or polyhalogenoalkyl group having 1 to 6 carbon atoms substituted by an alkoxycarbonyl group having 1 to 6 carbon atoms, a carbon substituted by a mono- or dialkylaminocarbonyl group having 1 to 6 carbon atoms Substituted with an alkyl group having 1 to 6 atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, a mono- or dialkylaminocarbonyl group having 1 to 6 carbon atoms, a cyano group, an alkylcarbonyl group having 1 to 6 carbon atoms (However, these phenyl The group and the benzyl group include a halogen atom, a trifluoromethyl group, a nitro group, an alkyl group having 1 to 6 carbon atoms,
It may be mono- or polysubstituted with an alkoxy group having 1 to 6 carbon atoms or an alkoxycarbonyl group having 1 to 6 carbon atoms. ), a 3- to 6-membered heterocycle (However, these heterocycles contain 1 to 3 heteroatoms selected from nitrogen atoms, oxygen atoms, or sulfur atoms in the ring. Also,
These heterocycles can be mono- or mono- or heterocyclic by a halogen atom, a trifluoromethyl group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkoxycarbonyl group having 1 to 6 carbon atoms. May be polysubstituted. ), 3- to 6-membered heterocycle (However, these heterocycles contain 1 to 3 heteroatoms selected from nitrogen atoms, oxygen atoms, or sulfur atoms in the ring. Also, these heterocycles include halogen atoms , trifluoromethyl group, nitro group, alkyl group having 1 to 6 carbon atoms, 1 carbon atom
It may be mono- or polysubstituted by an alkoxy group having 1 to 6 carbon atoms or an alkoxycarbonyl group having 1 to 6 carbon atoms. ) represents an alkyl group having 1 to 6 carbon atoms, R^1^2 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a carbon atom Number 2~
6 alkynyl group, phenyl group and benzyl group (however,
These phenyl groups and benzyl groups include halogen atoms, trifluoromethyl groups, alkyl groups having 1 to 6 carbon atoms,
It may be substituted with an alkoxy group having 1 to 6 carbon atoms or an alkoxycarbonyl group having 1 to 6 carbon atoms. ), and R^1^3 represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, and a benzyl group (however, these phenyl groups and benzyl groups are halogen atoms, trifluoromethyl groups, and alkyl groups having 1 to 6 carbon atoms. 6 alkyl group, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms,
It may be substituted with a nitro group. ), or R^1^2 and R^1^3 together with the nitrogen atom to which they are attached represent a saturated 5- to 7-membered heterocycle, or R^1^2 and R^1 ^3 represents a saturated 5- to 7-membered heterocycle with the oxygen and nitrogen atoms to which they are bonded, R^2^1 represents an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 3 to 7 carbon atoms. cycloalkyl group, alkyl group having 1 to 6 carbon atoms substituted by a cycloalkyl group having 3 to 7 carbon atoms, carbon substituted by a mono- or polyhalogenocycloalkyl group having 3 to 7 carbon atoms Alkyl group having 1 to 6 atoms, alkenyl group having 2 to 6 carbon atoms, alkynyl group having 2 to 6 carbon atoms, 1 to 6 carbon atoms
1 to 6 carbon atoms substituted by an alkoxy group of
an alkyl group having 1 to 6 carbon atoms substituted by an alkylthio group having 1 to 6 carbon atoms, a C 1 to 6 alkyl group substituted by a mono- or dialkylamino group having 1 to 6 carbon atoms; ~6 alkyl groups, mono- or polyhalogenoalkyl groups having 1 to 6 carbon atoms, mono- or polyhalogenoalkenyl groups having 2 to 6 carbon atoms, cyano groups having 1 to 6 carbon atoms substituted with an alkyl group, an alkyl group having 1 to 6 carbon atoms substituted with an alkoxycarbonyl group having 1 to 6 carbon atoms, an alkyl group having 2 to 6 carbon atoms substituted by an alkoxycarbonyl group having 1 to 6 carbon atoms; alkenyl group, alkyl group having 1 to 6 carbon atoms substituted with a mono- or dialkylaminocarbonyl group having 1 to 6 carbon atoms, alkoxycarbonyl group having 1 to 6 carbon atoms, and alkoxycarbonyl group having 1 to 6 carbon atoms; Mono- or dialkylaminocarbonyl group, cyano group, alkyl group having 1 to 6 carbon atoms substituted with an alkylcarbonyl group having 1 to 6 carbon atoms, alkylcarbonyl group having 1 to 6 carbon atoms, number of carbon atoms 1 to 6 mono- or polyhalogenoalkylcarbonyl groups, phenyl groups and benzyl groups (however, these phenyl groups and benzyl groups are halogen atoms, trifluoromethyl groups, nitro groups, alkyl groups having 1 to 6 carbon atoms, may be mono- or polysubstituted with an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms), a 5- to 6-membered heterocycle (however, these heterocycles may be substituted with nitrogen The ring contains 1 to 3 heteroatoms selected from atoms, oxygen atoms, and sulfur atoms.These heterocycles also include halogen atoms, trifluoromethyl groups, nitro groups, and alkyl groups having 1 to 6 carbon atoms. , which may be mono- or polysubstituted by an alkoxy group having 1 to 6 carbon atoms, or an alkoxycarbonyl group having 1 to 6 carbon atoms), and R^2^2 is a hydrogen atom, the number of carbon atoms R^2^3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R^2^4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; , a halogen atom, a mono- or polyhalogenoalkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted by an alkoxy group having 1 to 6 carbon atoms, and a halogen atom having 1 to 6 carbon atoms; Alkyl group having 1 to 6 carbon atoms substituted with alkenyloxy group, 2 carbon atoms
an alkyl group having 1 to 6 carbon atoms substituted by an alkynyloxy group of 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted by a mono- or polyhalogenoalkoxy group having 1 to 6 carbon atoms, C1-6 alkyl group substituted with C1-6 alkylthio group, C1-6 alkyl group substituted with C1-6 alkylsulfonyl group, cyano an alkyl group having 1 to 6 carbon atoms substituted with a group, an alkoxycarbonyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted by an alkoxycarbonyl group having 1 to 6 carbon atoms; group, number of carbon atoms: 1
-6 alkylcarbonyl group, 1 to 6 carbon atoms substituted by an alkylcarbonyl group having 1 to 6 carbon atoms
6 represents an alkyl group, R^2^5 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R^2^6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. , R^2^7 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and R^2^8 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. Mono- or polyhalogenoalkyl group, C1-C6 alkyl group substituted by C1-C6 alkoxy group, C2-C6 alkyl group
An alkyl group having 1 to 6 carbon atoms substituted with an alkenyloxy group having ˜6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted by an alkynyloxy group having 2 to 6 carbon atoms, and 1 carbon atom an alkyl group having 1 to 6 carbon atoms substituted with an alkylthio group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted by an alkylsulfonyl group having 1 to 6 carbon atoms, and a cyano group substituted with a cyano group; Alkyl group having 1 to 6 carbon atoms, having 1 carbon atom
~6 alkoxycarbonyl groups, C1-6 alkylcarbonyl groups, C1-6 alkyl groups substituted with C1-6 alkoxycarbonyl groups, C1-6 alkyl groups Represents an alkyl group having 1 to 6 carbon atoms substituted with an alkylcarbonyl group, L is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms. 6 represents an alkynyl group; an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a mono- or polyhalogenoalkyl group having 1 to 4 carbon atoms, a mono- or polyhalogenoalkoxy group having 1 to 4 carbon atoms; group, a halogen atom, and a monoalkylamino group having 1 to 4 carbon atoms. ] A sulfamide sulfonylurea derivative or a salt thereof. (2) A selective herbicide containing one or more of the compounds described in claim (1) as an active ingredient. (3) One or more of the compounds described in claim (1) and one of alachlor, acetochlor, metolachlor, primisulfuron, and nicosulfuron.
A herbicidal composition characterized by containing seeds as an active ingredient.