JPS5959669A - Cyclohexan-1,3-dione derivative, manufacture and herbicide composition - Google Patents

Abstract

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

Description

[Detailed description of the invention]

TECHNICAL FIELD The present invention relates to organic compounds exhibiting biological activity, particularly organic compounds having herbicidal and plant growth regulating effects, methods for producing such compounds, and methods useful for producing such compounds. The present invention relates to intermediates and herbicidal compositions and methods of using such compounds, as well as plant growth regulating compositions and methods of using such compounds. PRIOR ART The use of certain cyclohexane-11,3-dione derivatives as herbicides is known in the literature. For example, [Pesticide Manual]
e Manual) J [Worthing Editor (C
R~Vorthing gditor), The British Chrono Protection Carantil (The
Br1tfhCrop Protection Co
(uncil) No. 6) 1, 1979), the cycloderivative 1,3-noone conductor (methyl 3-[1-(allyloxyimino)butyl), known commercially as d-, aloxidimino sodium -4-hydroxy-6,6
-dimethyl-2-oxocyclohexy-3-enecarboxylate) and its use as a grass herbicide. This compound is covered by Australian Patent No. 4646.
No. 55 specification and its corresponding patents, such as British Patent No. 1
46 ] No. 170 Mei 1l (Book II and U.S. Pat. No. 39
No. 50420. The song was recently introduced at the 1980 British Crop Protection Conference [r1
980 Br1tish
Crop Protection Conference
ce-Weeds+ Proceedings Vol.
1. Re5earch Reports Month. pp. 39-46, British Chronograph Carancil, 1980), code name NP, 55
A new cyclohexane-1,3-noone herbicide [2-(N-ethoxyptrimidoyl)-5-(
Mention was made of 2-ethylthiodivir)-3-hydroxy-2-cyclohexen-1-one. This compound is described in Australian Patent Application No. AU-A I-35,3147
No. 78 and its corresponding application. Purpose of the invention The present invention provides novel cyclohexane-1, which has herbicidal activity.
The aim is to develop 3-dione derivatives. Structure and effects of the invention Novel cyclohexane-1 having a 5-pyrimidyl substituent
, 3-dione derivatives have been found to exhibit particularly useful herbicidal action. Therefore, the present invention relates to the general formula (I); 1 to 6 carbon atoms substituted with a substituent selected from the group consisting of roken, nitro group, hydroxy group, alkoxy group of 1 to 6 carbon atoms, and alkylthio group of 1 to 6 carbon atoms Alkyl group; number of carbon atoms: 2-
6 alkenyl groups; alkynyl groups having 2 to 6 carbon atoms; hydroxy groups: alkoxy groups having 1 to 6 carbon atoms; substituents selected from halo r and alkoxy groups having 1 to 6 carbon atoms; Alkoxy group having 1 to 6 carbon atoms substituted with a group; Alkenyloxy group having 2 to 6 carbon atoms; Alkynyloxy group having 2 to 6 carbon atoms; Alkanoyloxy having 2 to 6 carbon atoms Group: 1 for alkoxy group
-Alkoxycarbonyl group having 6 carbon atoms: alkylthio group having 1 to 6 carbon atoms; having 1 to 6 carbon atoms
Alkylsulfinyl group having 1 to 6 carbon atoms; Sulfamoyl group; N-alkylsulfamoyl group having 1 to 6 carbon atoms in the alkyl group; 1 to 6 in each alkyl group N having carbon atoms of
N-dialkylsulfamoyl group; hensyloxy group;
Benzene ring ＼rodan, nitro group, number of carbon atoms 1-6
alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and haloalkyl groups having 1 to 6 carbon atoms [substituted with 1 to 3 substituents] Pennoroxy group: group NR5R6 (in the formula R5 and R61
1, l: each independently selected from the group consisting of hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkanoyl group having 2 to 6 carbon atoms, a benzoyl group, and a benyl group);
selected from the group consisting of formyl and C2-C6 alkanoyl groups and their oxime, imine and Schiff base derivatives; R1 is hydrogen;
6 alkyl groups; alkenyl groups having 2 to 6 carbon atoms; alkynyl groups having 2 to 6 carbon atoms; alkyl groups or alkoxy groups having 1 to 6 carbon atoms; Alkylthio groups, phenyl groups and substituted phenyl groups (Hensen ring cabalodan, nitro group, cyan group, alkyl group having 1 to 6 carbon atoms, haloalkyl group having 1 to 6 carbon atoms, 1 to 6 carbon atoms) IPf 4iI+ with ~3 substituents selected from the group consisting of alkoxy groups and alkylthio groups of 1 to 6 carbon atoms)
16 substituents consisting of nitro group, cyano group, alkyl group having 1 to 6 carbon atoms, haloalkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, and 1 to 6 carbon atoms R2 is selected from the group consisting of a disubstituted benzenesulfonyl group substituted with 1 to 3 substituents selected from the group consisting of alkylthio groups; acyl groups; and inorganic or organic cations; Argyl group having 1 to 6 carbon atoms: 2 carbon atoms
~6 alkenyl groups; haloalkenyl groups having 2 to 6 carbon atoms; alkynyl groups having 2 to 6 carbon atoms; haloalkynyl groups having 2 to 6 carbon atoms: and alkyl groups having halocarbons, Alkoxy group having 1 to 6 carbon atoms, alkylthio group having 1 to 6 carbon atoms, phenyl group and benzene ring are halogen, nitro group, cyano group, 1 to 6 carbon atoms
6 (7) substituents selected from the group consisting of a furkyl group, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alkylthio group having 1 to 6 carbon atoms; an IN substituent selected from the group consisting of substituted phenyl groups substituted with 1 to 3 carbon atoms; Number 1 to 6 alkyl group, number of carbon atoms 1
~6 fluoroalkyl groups, carbon 3CJ"X number of molecules 2 to 6
alkenyl group, alkynyl group having 2 to 6 carbon atoms, and phenyl group, and R4 is hydrogen, haloke9, cyano group, and 1 to 6 carbon atoms;
The present invention provides compounds having 1 to 6 alkyl and alkoxy groups (selected from the group consisting of alkoxycarbonyl groups having ll carbon atoms, and n representing all integers from 1 to 3).General When in the compound of formula (1) X is selected from formyl and alkanoyl groups of 2 to 6 carbon atoms and their oxime, imine and Schiff base derivatives, the nature of the oxime, imine and Schiff base derivatives is This is not narrowly limited. Although I do not intend to be bound by theory, it is believed that the imine group (1st revision) is removed in plants.
This is believed to give the corresponding compound of general formula (I) in which X is a formyl group or an alkanoyl group having 2 to 6 carbon atoms. Suitable forsyl and C2-C6 alkanoyl groups and their oxime, imine and Schiff base derivatives have the formula -C(R)=NR, where R is hydrogen and C1-5 selected from alkyl groups having 1 to 6 carbon atoms, hydrogen, alkyl groups having 1 to 6 carbon atoms, phenyl groups, benzyl groups, hydroxy groups, alkoxy groups having 1 to 6 carbon atoms, phenoxy groups, and benzyloxy groups. (selected from ). In general formula (1), when R is selected from acyl groups, the nature of the acyl group is not narrowly limited. Without intending to be bound by theory, if R1 is an acyl group, the acyl group is removed by hydrolysis in the plant to form R.
This is believed to give rise to the corresponding compounds of general formula (1) in which 1 is hydrogen. Suitable acyl groups are alkanoyl groups, e.g.
~6 alkanoyl-11-; aroyl crab example benzoyl: ;i! and benzene ring is halodane, nitrono5. Cyano group, alkyl group having 1 to 6 carbon atoms, haloalkyl group having 1 to 6 carbon atoms, 1 to 6 carbon atoms
an IM′-substituted benzoyl group substituted with 1 to 3 substituents selected from the group consisting of alkoxy groups and rF alkylthio groups having 1 to 6 carbon atoms; and heteroaroyl groups, such as 2-furoyl groups, (,3-furoyl group, 2
-Thenoyl group and 3-thenoyl group. In the compound of general formula (1), when R is selected from turnips or organic cations, the nature of the cation 'tI'J is not narrowly limited. Without intending to be bound by theory, when R is a cation, jg,'i ions are removed in 4)f(formula (1) where Iζ is hydrogen).
It is thought that all of the compounds are generated. Suitable cations include ions of alkali metals and alkaline earth metals, heavy metals, including transition metal ions, and ammonium ions. A suitable organic cation is formula B9
R10R11n 12Z (in the formula R9, RI Q, R1
1 and R are each independently hydrogen; a substituent selected from iv from 717i consisting of an alkyl group having 1 to 10 carbon atoms, halogen, and an alkoxy group having 1 to 6 carbon atoms; tt4P
iFt-substituted alkyl force of 01 to 10 carbon atoms; phenyl group: penzyl, l&; and hibenzene ring, nitro group, cyano group, alkyl group of 1 to 6 carbon atoms, carbon 1 atom number 1 Consists of ~6 haloalkyl groups, alkoxy groups having 1 to 6 carbon atoms, and alkylthio groups having 1 to 6 carbon atoms! 1-3 selected from 11
(selected from the group consisting of a 1-F-substituted phenyl group and a 1-Y-substituted benzoyl group) substituted with IFq substituents. The compound of the present invention is also represented by the following formula:
However, in the formula, φ exists in the isomeric form of the unexploded "su" when the group R1 is hydrogen (IZ combination 9 of course, the descending self is any of the four tautomorphic convoluted forms J1 force 1 fl Existence as !-t(Ila') (anus)(
11c) (IId)
Also, examples include alkyl groups having 1 to 6 carbon atoms, carbon alkoxysts having 1 to 6 carbon atoms, alkyl groups having 1 to 6 carbon atoms, 710 carbon atoms, carbon atoms having 1 to 6 carbon atoms; Haloalkyl groups, amino groups, alkylamino groups having 1 to 6 carbon atoms and di(alkyl)amine groups containing 1 to 6 carbon atoms in each alkyl group are suitable. As R1, water 1: alkyl group having 1 to 6 carbon atoms: alkenyl group having 2 to 6 carbon atoms: 2 to 6 carbon atoms;
6 arginyl groups; an alkyl group having 1 to 6 carbon atoms; an alkylthio group having 1 to 6 carbon atoms; a phenyl group;
A group consisting of a cyano group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alkylthio group having 1 to 6 carbon atoms. Substituted alkyl group having 1 to 6 carbon atoms substituted with a substituent selected from the group consisting of a substituted phenyl group substituted with 1 to 3 substituents selected from: 1 to 6 carbon atoms alkylsulfonyl group; benzenesulfonyl group: benzene ring is halogen, nitro group, cyano group, alkyl group with 1 to 6 carbon atoms, 1 to 6 carbon atoms
substituted with up to 3 substituents selected from the group consisting of 1-6 alkyl groups, alkoxy groups of 1 to 6 carbon atoms, and alkylthio groups of 1 to 6 carbon atoms. W-substituted benzenesulfonyl group Niacyl group; inorganic or organic cations are suitable. R2 is an alkyl group having 1 to 6 carbon atoms; a fluorenyl group having 2 to 6 carbon atoms;

[λ number of children 2-6
haloalkenyl group having 2 to 6 carbon atoms; alkynyl group having 2 to 6 carbon atoms; haloalkynyl group having 2 to 6 carbon atoms: an alkyl group in which the alkyl group is a halogen, an alkoxy group having 61 to 6 carbon atoms, carbon Alkylthio group having 1 to 6 atoms, phenyl group and benzene ring is halokene, nitro group, cyan group, argyl group having 1 to 6 carbon atoms, 1 to 6 carbon atoms
1 to 3 substituents selected from the group consisting of haloalkyl groups, alkoxy groups of 1 to 6 carbon atoms, and alkylthio groups of 1 to 6 carbon atoms; Suitable are 115'-substituted alkyl groups having from 1 to 6 carbon atoms substituted with a t substituent selected from the group consisting of 4-inhibited phenyl groups. As R3, number of carbon atoms] ~6 alkyl group: carbonaceous atom; fluoroalkyl group with 1 to 6 carbon atoms; number of carbon atoms 2~
6 alkenyl groups: alkynyl groups having 2 to 6 carbon atoms: and phenyl groups are suitable. Suitably R4 is hydrogen. n (i is suitably an integer of 1 to 3. In preferred compounds of the present invention, X is each independently an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, Alkylthio group having 1 to 6 carbon atoms, alkylsulfinyl group having 1 to 6 carbon atoms, alkylsulfonyl group having 1 to 6 carbon atoms, halodane, amine group, 1 to 6 carbon atoms in alkyl group selected from the group consisting of N-alkylamino groups having 1 to 6 carbon atoms in each alkyl group; Alkanoyl group: benzoyl group and benzene ring cabalodan, nitro group, alkyl group having 1 to 6 carbon atoms, and alkoxy group having 1 to 6 carbon atoms 1 to 3 moeken groups
Substituted benzoyl group substituted with: a benzenesulfonyl group and a benzene ring selected from the group consisting of a halocarne, a nitro group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. 1-3 11
Slightly substituted benzenesulfonyl groups substituted with substituents: and alkali metals such as lithium, potassium and sodium, alkaline earth metals such as magnesium, calcium and barium, transition metals such as manganese, copper, zinc, iron, nickel. , Comi 4 Rut and 4Q, ammonium ions and tri- and tetra-(alkyl)ammonium ions (alkyl groups are from alkyl groups having 1 to 6 carbon atoms and hydroxyalkyl groups having 1 to 6 carbon atoms -JIARsh) R2 is an alkyl group having 1 to 6 carbon atoms, or 2 carbon atoms;
~6 alkenyl groups, alkynyl groups having 2 to 6 carbon atoms, no-roalkyl groups having 1 to 6 carbon atoms, carbon,
7-lorkenyl group having 2 to 6 atoms and 2 carbon atoms
R3 is selected from alkyl groups having from 1 to 6 carbon atoms, R4 is selected from hydrogen and rhodane, and n is selected from 1 to 3; A more preferable compound of the present invention is a compound in which the pyrimidine ring is bonded to the cyclohexane ring at the 5-position. That is, general formula (■): [In the formula, X is each independently an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms.
6 alkoxy groups, alkylthio groups having 1 to 6 carbon atoms, alkylsulfinyl groups having 1 to 6 carbon atoms,
Alkylsulfonyl group having 1 to 6 carbon atoms, )・rodan, amino group, N-alkylamino group having 1 to 6 carbon atoms in the alkyl group, and having 1 to 6 carbon atoms in each alkyl group selected from the group consisting of N,N-di(alkyl)arymino groups, R1 is hydrogen; alkanoyl groups having 2 to 6 carbon atoms, benzoyl groups, alkali metal ions, transition metal ions, ammonium ions and ~ and tetra-(alkyl)
ammonium ion (the alkyl group is selected from alkyl groups of 1 to 6 carbon atoms and hydroxyalkyl groups of 1 to 6 carbon atoms), and R2 is selected from the group consisting of 3 alkyl groups, 1 carbon atom
-3 selected from the group consisting of haloalkyl, allyl and hyhaloallyl, R3 is selected from alkyl groups of 1 to 3 carbon atoms, R4 is hydrogen, and n is from 1 to 3; a is a selected integer]. More preferred compounds of the present invention include pyrimidine ring 2-
Included are 5-pyrimidyl compounds substituted at the 4-, 4- and 6-positions. That is, X is each independently an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, and each alkyl group having 1 to 6 carbon atoms. N, N-di(
alkyl)amino group, R1 is selected from the group consisting of hydrogen, an alkanoyl group having 2 to 6 carbon atoms, and an alkali metal ion, and R2 is an alkyl group having 1 to 3 carbon atoms, an allyl group; and haloallyl group, and R3 has 1 to 3 carbon atoms.
Compounds of general formula (III) are preferred, wherein R4 is hydrogen and n is an integer of 3. Further preferred compounds of the present invention include 5-pyrimidyl compounds substituted with tR at the 2-position of the pyrimidine ring, that is, general formula (Illa): 6 alkyl groups, alkoxy groups having 1 to 6 carbon atoms, alkylthio groups having 1 to 6 carbon atoms, alkylsulfinyl groups having 1 to 6 carbon atoms, and 1 to 6 carbon atoms in each alkyl group. R1 is selected from the group consisting of hydrogen, alkanoyl groups of 2 to 6 carbon atoms, and alkali metal ions, and R2 is selected from the group consisting of N,N-di(alkyl)amine groups having a number of carbon atoms. 1 to 3 alkyl groups, allyl groups and haloallyl groups, R5 is selected from alkyl groups having 1 to 3 carbon atoms, and R4 is hydrogen. Particularly preferred X is a methyl group, methoxine'+K
, a methylmercaptomino group. Particularly preferred values for R1 include hydrogen, alkanoyl groups having 2 to 6 carbon atoms, sodium and potassium. Particularly preferred R2 are ethyl group, n-propyl group, allyl group and chloroallyl group. Particularly preferred R5 is Mononoke, ethyl group and n-propyl group. Examples of compounds encompassed by the present invention are listed below: (JL
;ti5 (J0 Specific examples of compounds of the invention are listed in Tables 1ap and 1b, Table 1
Table a Table 1a Continued Table 1b The compounds of the present invention can be produced by various methods, and in another aspect, the present invention provides a method for producing the compound of general formula (1). For convenience, the preparation of the compounds of the invention can be considered in three or four parts. Part A is 5-arylcyclohexane of general formula (IX)
Concerning the production of 1,3-dione. This reaction can be carried out in a two-step process according to methods (i) to (iii) below. (1) Preferably in the presence of a base, the aldehyde derivative of the general formula (7) is reacted with the acetone of the general formula (IV & ) or the acetone derivative of the general formula (tvb), respectively. ) to produce a ketone derivative of
The ketone derivative of general formula (Ma) is reacted with the malonic ester trace conductor of general formula (Ma), preferably in the presence of a base, or the ketone derivative of general formula (Vlb)'it
MZ is reacted with a malonic acid ester derivative of formula (■b), and in the general formula (Ma) or formula b) produced respectively [■
' is isolated or hydrolyzed directly, preferably in the presence of an acid, to yield the 5-arylcyclohexane-1,3-dione of general formula (IX), or preferably in the presence of a base. , a ketone derivative of the general formula (Ma) is reacted with an alkanoic acid ester of the general formula (■C) to obtain the general formula (
IX) 5-arylcyclohexane-1,3-dione is produced. (11) Preferably in the presence of a base, the aldehyde derivative of general formula (V) is reacted with the malonic acid ester of general formula (■b) to produce an arylmethylidene malonate derivative of general formula (Me), which is then reacted with an acetoacetate derivative of general formula (■d), preferably in the presence of a base, and the resulting intermediate of general formula (■C) is converted to 11iI￥
5-arylcyclohexane-1 of the general formula (IX) by hydrolysis or directly, preferably in the presence of an acid.
(1i) Preferably in the presence of a base, an aldehyde derivative of general formula (V) is reacted with an acetate ester of general formula (■c) to form a 3-dione of general formula (Me). A 2-alkenoate derivative is formed which is then treated, preferably in the presence of a base, by
The intermediate of the general formula (Ma) formed by reaction with an acetoacetate derivative of the general formula (■d) is isolated or directly hydrolyzed, preferably in the presence of an acid, of the general formula (IX
) to produce 5-arylcyclohexane-1,3-dione. Part B is formed by acylating the compound of the general formula (IX) to form the compound of the general formula (IX).
■) 2-acyl-5-arylcyclohexane-1,
It relates to a reaction that produces 3-dione. This reaction converts the 5-arylcyclohexane-1,3-dione of the general formula (■) into (iV) the corresponding alkali metal salt of the general formula (XI) or the alkoxide salt of the general formula (XII) (in the formula M is an alkali metal ion, and R has 1 to 6 carbon atoms.
or (V) with an acid anhydride of general formula (X) in the presence of a corresponding acid of general formula (XIV). or (vi) in the presence of a Lewis acid catalyst, an acid halide of the general formula (X'l, where hal represents a halogen)
or (Vll) acid halide of general formula (XV) and general formula (X
(viii) with a hydride of an alkali metal or alkaline earth metal and then with an acid anhydride of the general formula (X) or an acid of the general formula (XV). This can be carried out by reacting with a halide. In addition, this acylation reaction can be carried out as follows (ix) to (xii)
): (!X) 5-arylcyclohexane-1,3-,'one of general formula (D
V) is reacted with an acid halide of general formula (XVI) to produce an intermediate O-acyl derivative of general formula (XVI),
) is reacted with a Lewis acid catalyst, or (x1) an intermediate of general formula (XV[) is reacted with general formula (XIV)
or the intermediate of general formula (XVI) is reacted with imidazole. Part 0 relates to the formation of compounds of the invention of general formula (I) in which R,1 are hydrogen, ie compounds of general formula (n). This reaction involves reacting 2-acyl-5-arylcyclohexane-1,3-dione of general formula (■) with (Xiii) an alkoxyamine derivative of general formula (X■), or
Or, by reacting with hydroxylamine to form the general formula (X
■) to generate an intermediate oxime conductor with the general formula (
The intermediate oxime visiting conductor of X■) is treated with an alkylating agent of the general formula (X■) (wherein is a group to be eliminated, such as chlorine, bromine, iodine, sulfate, nitrate, methyl sulfate,
ethyl sulfate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, methanesulfonate, fluorosulfonate, fluoromethanesulfonate and trifluoromethanesulfonate). Part D relates to the preparation of compounds of the invention of general formula (I) in which R1 is a substituent other than hydrogen. Compounds of the invention of the general formula (I) in which R forms an ether, acyl or sulfonyl derivative of a compound of the general formula (■) can be obtained from the corresponding compounds of the invention of the general formula (If) by the compound of the general formula (XX). It can be produced by reacting with an etherification reagent, acylation reagent or sulfonylation reagent. The compounds of the present invention of the general formula (1) in which R is an inorganic or organic cation are the compounds of the present invention of the general formula (I) in which R1 is hydrogen, that is, the corresponding compounds of the present invention of the general formula ([1)] It can be produced from a compound of general formula (II) by reacting it with an all-inorganic or organic salt of the compound of general formula (II). For example, a compound of general formula (1) in which R1 is an alkali metal ion can be produced by reacting a suitable compound of general formula (I[) with a suitable alkali metal hydroxide or alkoxylate. Compounds of general formula (1) in which R1 is a transition metal ion or an organic cation can be prepared by reacting a suitable compound of general formula (If) with a suitable transition metal salt or organic base. can. Furthermore, compounds of general formula (1) in which R is a transition metal ion or an organic cation can be obtained by reacting a suitable compound of general formula (I) in which R1 is an alkali metal ion with a suitable transition metal salt or organic base. It can be manufactured by Therefore, the present invention also provides a method for producing the compound of the general formula (1), which method comprises the general formula (X
1ll) 2-acyl-5-(aryl)cyclohexane-1,3-dione g conductor is reacted with an alkoxyamine derivative of general formula (X) to produce a compound of the present invention of general formula (U) , or a 2-acyl-5-(aryl)cyclohexane-1,3-dione reading conductor of the general formula (XI[I) is reacted with hydroxylamine to form a compound of the general formula (X
The oxime intermediate of the general formula (I
t) of the present invention, and optionally, a compound of the general formula (
XX) to form a compound of the invention of general formula (I). 4 CH3COCH5CI(3COCH2RcH3co2R
(IVa) (IVb)
(IVc) φ-CH0 (V) φ-CH=CH-C0CI (3φ-CH=CR-COC
H. (Via) (■b)φ-CH
=C(Co2R)2 φ-CH=CH-C02
R(Vlc) (Via)RC
H(C02R)2CH2(Co2R)2(Wa)
(■b) RCH2Co2RCH3C0
CHR'C02R ('41c) (
■d) (Wa) (■b) (■(ri (IX) (RCo)20 RCo2M ROM (X)
(XI) (Xl[)(Xll
l) R3CO2)T RCoh a 1(X
IV) (XV)H,,N0R
2R2L I? , L(Xν11)
(XiX) (XX) (XVIII) General formula (V), (Wa), (＼rib), (Via), (
■d), (Ml:a), (■b), (■C),
(■) Some of the intermediate compounds of (X V
lb), (VIc), ld), (MIla), (■ib
), (■C), (IX) (Xlll), (XVI) and (XMTI) o New compounds and methods for producing the same are provided. For example, f19. used in the production of the compound of general formula (1).
' The pyrimidine carboxaldehyde of formula (V) is the ! It, i.e., 2,4.6-)dimethoxypyrimidine-5-carboxaldehyde has already been published in B. Therefore, the present invention further provides the general formula (■): [wherein X and n
represents the above, or when X is a methoxy group, r(
provides all compounds where n is not equal to 3. In the compound of the general formula (1), a- can be made into a simple one by forming a novel 2-substituted-pyrimidine-5-calyFxaldehyde. Accordingly, the present invention further provides bi-I-nominone-5-carbo:V dialdehydes of the general formula (Va): [wherein X is all 2'.--J]. Compound 2,4.6-trimethoxypyrimidine-5-carboxaldehyde i-,N,,N-dimethylpolamide and 2,4°6-trimethoxypyrimidine' (i: Bylsma Year (Vi ls)
Mayer) method. However, it is effective only when using compounds such as ``4. Ring K i7p ↑I11. 71~' due to the presence of three child horse groups. Pyrimidine has a strong electron - I: The pyrimidine carboxaldehyde that is not activated by the j group is flattened! j
It is possible to use Vilsmeier's formylation reaction to obtain \j. For example, among the compounds of the general formula (Il), the novel 2--virimidi-7-5-carboxaldehyde used in the production of a preferable compound is the sister of the new method IJEkeF1. The new method involves deriving 2-(methylene)propanediilidene and reacting it with, for example, H'(2-C(dimethylamino)methylene]-propanediilidene)bis[dimethylammonium verchlorate]amidine X4. Therefore, the present invention further provides the general formula (Va)
: Regarding the method for producing a pyrimidine-5-carboxaldehyde derivative of 7, the method comprises a 2-(methylene)propanediylidene derivative of the general formula (XXI) in which It is selected from an alkyl group having 1 to 6 carbon atoms. is reacted with an amidine derivative of the general formula (XXU) in which X is as defined above. The following margins (XX I ) (XXn) Invention I/:1 Furthermore, the compound 11 of the general formula ([): [in the formula, x, n,' and G are those of 111 > r + S], I whole culm I, do it, do you want to do it? , t, 1, and 1, furthermore, the general formula (Xll+) [in the formula, The compound t of (ii) is active as a descaling agent], therefore, the present invention also provides a compound of formula (1) comprising applying an effective amount of the compound of general formula (1) to the plant or the growth medium of the plant. It provides a method for significantly damaging or killing desired plants. Generally, the compound of general formula (T) exhibits herbicidal activity against divine plants. However, some of the compounds of the invention 1,
It is selectively active against monocotyledonous plants, and dicotyledonous plants are relatively less susceptible to application of the compounds of the present invention at rates that would cause significant damage or death to other plant species. not be harmed by. Furthermore, some of the compounds 1 with the general formula
It is selectively active only within 1(q;)J and can be used in moths 4 sufficient to control monocots in cultivated crops, especially in cereals. Certain of the compounds of the present invention are useful in commercially for the control of wildflowers, such as wild oats and rye, in cultivated monocotyledonous crops, such as wheat, barley and various other cereals. be. Therefore, the present invention further provides a method for controlling monocot grasses in cultivated crops, especially cereal crops, e.g. ) before administering nL of the compound of general formula (1) to the body, and then ingesting outside plants.
1) If the force is sufficient to cause damage or damage to the crop, but not enough to damage the crop lengthwise, it will wilt. The uninvented 5-(pyrimidyl)cyclohexylion in which the pyrimidine base j has three fr+:conversions; Surprisingly, it is clear that 4'11 indicates a high level of exclusion and/or I-G C (selective exclusion).
-0On the other hand, there is one pyrimidine ring, 2
The present invention's 5-(pyrimidyl)cyclohexyl-non-1,3-noone tt4 conductor having a 1νS substituent of ilJ,l has high scavenging activity and Q1g frequency 3f(4i (removal Y antiquity) at the same time. (C) Generally, the compound of general formula (1) is directly added to the proboscis. IJsu (hfti month after germination) or Matagae' 7 rules, 4119 Before germination of Matsu, 1・zu (blade ``rl! After the ship has been launched, a single piece may be added, depending on the case.
'・41-Takaderuru. In order to suppress the growth of plants, the compound of general formula (1) is
Iirf'L? < tH can be used to injure or kill, solid or d
It is preferred to use the compounds of the present invention in compositions in admixture with compatible materials, including liquid diluents. Therefore, the present invention further provides a composition for inhibiting growth, inhibiting plant damage or killing plants, which contains the compound of the general formula (1) described above and a stimulatory substance that can be used to deceive agriculture. Some of the compounds of general formula (1) are useful), gi′
Shows regulatory activity in snout growth. For example, compounds of general formula (I) are herbicides which are selectively active against wild reeds in cultivated crops at certain application rates; , indicating j-node action. Plant growth regulation effects occur in many ways. Examples include suppression of apical dominance, stimulation of axillary growth, stimulation of early flowering and 1Φ offspring formation, increased flowering and increased seed yield,
There is stem enlargement, stem shortening and tillering. Plant growth H171 nodal effects exhibited by the compounds of the invention include tillering and stem shortening in crops such as wheat and barley. bY refers to the present invention, which further provides a method for growing plants; It consists of applying the effective use of J~. In order to carry out the whole method of one-product growth method of the present invention, the compound of general formula (1) is applied directly to the plants (for 17Ii after germination) or one set of 11 seeds or 1" to the soil before the germination of the plants. (For pre-emergence mI) 'MII can be used.The compounds of general formula (1) can be used alone or with solid or liquid diluents to control the growth of plants. It is preferable to use the compound of the present invention in the form of a composition containing the compound of the present invention mixed with a carrier a. Fj4 dark - A finger containing seasonal drawing material 1 (+ material growth training r1 composition) which can be numbered in fj4 dark. The composition of the invention may be in solid, liquid or yeast form. .The composition contains 1 serving, 1 serving, 1 serving and 9 wet ingredients, which requires dilution before use.Therefore, the concentration of active ingredient in the composition of the present invention may vary by 1 serving. , the type of formulation and whether the composition is ready for use, for example, as a dust or aqueous emulsion;
A thick material suitable for diluting to 1, for example an emulsifiable material
! It varies depending on whether it is buried or used as an irrigation agent. in general,
The compositions of the present invention contain from 1 ppm to 99 parts by weight of total active ingredients. Solid compositions may be in the form of powders, dusts, pellets, granules and granules containing the active ingredient in admixture with solid diluents. Powders and dusts H can be prepared by mixing or grinding the active ingredient with a solid carrier material to produce a finely divided composition. Granules, granules, and takuret, for example, U”
It can be prepared by coating or impregnating a preformed granular solid carrier material with the active ingredient, or by bonding the active ingredient to a solid support strip by means of a S[i catalyst. The lower margin solid support 'S includes, for example, mineral earths and clays such as kaolin, bentonite, porous diatomaceous earth, Fuller's earth, atakulay, diatomaceous earth, bolus clay, l/s, talc, chalk, dolomite, Limestone, lime, □calcium carbonate, ground magnesium, magnesium oxide, ammonium sulfate magnesium, stone, silica, silicic acid, silicates, and silica dal; ammonium filets, ammonium phosphates, ammonium nitrates and urea; natural products of vegetable origin, such as grain meal and flour, bark flour, wood grain flour, nut flour and cellulose flour; and synthetic polymers Ipj, such as ground or powdered gristine. ,
It is oil and oil. Still January/January": Composition includes active ingredient and solid J1"
Possessing a wetting agent, an emulsifier and/or a surfactant that acts as a shaving agent (mixed with IR or higher to facilitate the dispersion of active ingredients in a liquid)
1. Hydrable dust may be in the form of powder, granules or coarse particles. Cationic surfactants include quaternary ammonium compounds such as long chain alkyl ammonium salts such as cetyltrimethylammonium bromide. Anionic surfactants include soaps or fatty acids. Alkali metal salts, alkaline earth metal salts and ammonium salts, alkali metal salts, alkaline earth metal salts and ammonium salts of lignin sulfonic acid; naphthalene sulfonic acid furnaces, e.g. Including alkali gold salts of arylsulfonic acids, alkaline earth metal salts and ammonium salts, salts of condensation products of sulfonated naphthalenes and naphthalene derivatives with formaldehyde, sulfonated naphthalenes and naphthalene derivatives with phenol and formaldehyde. salts of condensation products and salts of alkylarylsulfonic acids, such as dodecylbenzenesulfonic acid;
Included are the alkali metal, alkaline earth metal and ammonium salts of sulfuric acid or alkyl sulfates, such as long chain monoesters of lauryl sulfate and monoesters of sulfuric acid and fatty alcohol glycol ethers. nonionic surface fF
' = External cutting is the synthesis of ethylene oxide with fatty alcohols, such as VI' oleyl alcohol and hiscetyl alcohol. Condensation product; 1) Condensation product of ethylene oxide and mustard oil; Long-chain fatty acid and hexit anhydride, e.g. (1) Partial ester derived from sorbitan monolaurate,
and its condensation product IJlV with ethylene oxide;;
Ethylene oxide/pro2 oxide block copolymer; poor uryl alcohol, ]? I) Reciprocal Nidecyl acetal; and lecithin. ]・Notification'l'1 A liquid composition is formed from a solution or dispersion of the active ingredient in a liquid carrier material, optionally containing one or more surfactants acting as wetting agents, emulsifying agents and/or dispersing agents. Anything that consists of it is fine. Liquid support substances include, for example, water; mineral oil fractions, such as kerosene, solvent naphtha, petroleum, coal tar oil and aromatic petroleum fractions; aliphatic, cycloaliphatic and aromatic hydrocarbons, such as mother roughhein, cyclohexane, toluene. , xylene, tetrahydronaphthalene and alkylated naphthalenes; alcohols such as methanol, ethanol, pro-yanols, isopropanol, butanol, cyclohexanol and globylene glycol; ketones such as cyclohexanone and isophorone; strong polar organic solvents, e.g. These are dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone and sulfolane. Preferred liquid compositions are aqueous suspensions, dispersions or emulsions of the active ingredients, which are suitable for application by spraying, misting or sprinkling. Such aqueous compositions are generally prepared by mixing concentrated compositions with water. Suitable concentrated compositions are emulsion concentrates,
Includes pastes, oil dispersions, aqueous suspensions and aqueous solutions. ``Mother Thick Thickness I'': Generally, it is necessary to withstand long-term storage and to be able to be diluted with condensate from such storage for a sufficient period of time to form an aqueous formulation that is homogeneous and can be applied with conventional spray equipment. be. Advantageously, the concentrates contain 20-99M 1% of active ingredient, preferably 20-60% by weight. Emulsions or emulsifiable concentrates are advantageously prepared by dissolving the active ingredient in an organic solvent containing one or more surfactants. The paste can be prepared by combining the finely divided active ingredient with a finely divided solid support material, one or more surfactants, and optionally an oil. The oil dispersion contains the active ingredient, a hydrocarbon oil and 1
It can be produced by grinding the surfactant 'c-fta' into a sec or more surfactant. Aqueous concentrated suspensions can be suitably prepared by sol-milling a mixture of the active ingredient, water, at least one surfactant and preferably at least one suspending agent. Suitable suspending agents include hydrocolloids, such as poIJ (N-vinylpyrrolidone), sodium chloride, and sodium chloride. oxymethylcellulose and vegetable gums, such as gum arabic and tragantacom;
Hydrated colloidal mineral silicates such as montmorillonite, paiprite, nontronite, hectorite,
sabonite, sauconite l-, l-bentonite: other cellulose derivatives; and poly(vinyl alcohol). Wettable powder concentrates are advantageously prepared by mixing together the active ingredient, one or more solid carrier materials, and optionally one or more suspending agents, and grinding the mixture into a powder of a given particle size. can be manufactured. Aqueous suspensions, dispersions or emulsions can be prepared from the concentrated composition by mixing the concentrated composition with water, optionally containing a surfactant and/or an oil. It should be noted that compounds of the invention of general formula (1) in which R1 is hydrogen are acidic. Therefore, - size 11 type (
1) The compound of formula (7) can be used as a TmC or an unframed base group.A compound of the general formula (1) of Hayabusa no Sen is formulated or used. In particular, the salt itself, i.e., the general formula (I) in which R1 is an open or framed cation;
or compound 1 of the general formula (1) in which d1 (1 is hydrogen) is used in the formulation (7 suitable compounds (P
Alternatively, a falcon can be produced with its "μ" by using a comb. Solid compositions can be applied by dusting or any other means suitable for dispersing or dispersing solids. The rate of application of the compounds of the invention can be determined by, for example, the compound selected for use, the growth inhibiting It depends on the nature of the plant to be used, the formulation chosen for use 1, and whether the compound is absorbed through the leaves or used for absorption through the roots.However, in general As a standard, an application rate of 0.005-20.9 kg per hectare is suitable, and an application rate of 0.01-5.Q kg per hectare is preferred. In addition to compounds of the invention, compounds of the invention may include one or more compounds that are not compounds of the invention but have biological activity. For example, as noted above, compounds of the invention generally include dicotyledonous 44r ( or broad-leaved 4'IF (1), it is significantly more effective against monocotyledonous plants or grasses (11). However, even if the herbicidal compound of the general formula (1) shown in ^11 is used, it may not be sufficient to protect the crop I and η. and at least one other herbicide.The other herbicide is an optional herbicide that does not have the general formula (1)'f, In general, the other herbicides i'i11 are herbicides with supplementary action.The bright seeds 1 are, for example, mixtures containing herbicides active against broad-leaved weeds.Second preference 4: +lj J, I'i is a mixture containing a contact herbicide. A, Pengu 2,1.3-Thyanozin-4-one-2
, 2-monooxide Jh-i, 1siIJ e.g. 3-isofurobylbenzo-2,1,ni-3-cyanoazine-4-
-2,2-dioxide (-crotch pendazone), B, Hormone VQ Grass nil and H'lniphenoxyalkane t'3P +11% 1'', 1 and 4-chloro-2-methylphenoxyacetic acid (- Crotch MCPA), 2
-(2,4-dichlorophenoxy)noropionic acid (-crop dichlorogloso), 2,4.5-)dichlorophenoxyacetic acid (-crop 2,4,5-'r), 4-(4
-chloro-2-methylphenoxy)butyric acid (-crotch MCP
B), 2,4-dichlorophenoxyacetic acid ゛(-crotch 2.4-D), 4-(2,4-dichlorophenoxy)
Butyric acid (-crotch 2.4-DB), 2-(4-chloro-2-
methylphenoxy) propylene ridge (-crotch mecogloa a), and these inducers) j lunch break (e.g. salt, ester,
amide, etc.), C,3-[4-(halophenoxy7)phenyl]-1,1-sialygylurea, e.g. 3-[4-(chlorophenoxy)phenyl]-1,1-tumethylurea (
-grain temperature chlorooxyuron), D, dinitrophenols and their derivatives (e.g. vinegar polyester), 1+1
1, 2-methyl-4,6-nonitrophenol (-crotch DNOC), 2-tBt-butyl-4,6-dinitrophenol (-crotch/horn tarp), 2-5ee-butyl- 4゜6-nonitrophenol (-crotch/zonoseb)
and its nitol, dinoceb acetate, E, nonitropnyline herbicides, e.g. ) nitramine)
, 2,6-nonitro N, N-diglobyl-4-trinorolomethylaniline (common name trifluralin) and 4
-Methylsulfonyl-ruaniline (-crotch nitranine), F. Phenyl urea herbicide, N'-(3.4
-dichlorophenyl)-N,N-trimethylurea (common name diluone) and N,N-trimethyl-N'- (3-
( ) IJFlu A lomethyl) pheninoto] urea (-
groin fluometuron), G. Phenylcarbamoyloxyphenolcal/<Gut force 1, e.g. 3-[(methoxycarbonyl)amine]phenyl(3-ethylphenyl)-force) (-
Jl phenmesophane) and H3-[ethoxycarbinyl aba)] phenyl phenyl carbamate (generic name desmedifane), H. 2-phenylpyridazin-3-one, such as 5-agono-4-chloro-2-phenylpyridazin-3-one (generic name pyrazone) ■. Uracil herbicides, such as 3-cyclohexyl-5.
6-drimethyleneuracil (generic name Renacil), 5-bromo-3-Bec-butyl-6-methyluracil (
-crotch bromacil) and 3-tart-butyl-45-
Chloro 6-medyluracil (-crotch terpacil), J. l-rhianone herbicide, e.g. 2-chloro-4=
Eddylamino-6-(isofurobylamino)-1,3
．． 5-trianone (-crotch atranon), 2-chloro-
4,6-(ethylamine)-1. 3,5-triazine (common name simin) and 2-azido-4-(isonorobylamino)-6-methylthio-1.
3.5-) riazine (-crotch anozoloptrine), K. 1-Alkoxy-2-alkyl-3-phenylurea herbicides, such as 3-(3+4-·cycloaphenyl)-1-methoxy-1-methylurea (generic name Linuron)
, 3-(4-chlorophenyl)-1-methoxy-1-methylurea (common name monolinuron and 3-(4-bromo-
4-chlorophenyl)-1-methoxy-1-methylurine I
AC8 name chlorobromulon), L, thimecarbame-1 herbicide, e.g.
, M, 1.2.4-triazin-5-one, e.g. 4-amino-4,5-dihydro-3-methyl-6-phenyl-
1,2,4-)riazin-5-one (-crotch metamitron) and 4-amino-(3-tert-butyl-4,5
-dihydro-3-methylbu-o-1.2.4-)riazin-5-one (-crotch metripsin), IJ, tezoic acid herbicides, e.g. 2 + 316-
)! J dichlorobenzoic acid common name 2,. 3, 6-T
BA), 3° (5-dichloro-2-methoxybenzoic acid (
3-amino-2,5-dichlorobenzoic acid (common name chloramben), O, aniline herbicides such as N-butoxymethyl-α-
Chloro-2/, 6/-noedylacetanilide (generic name butachlor), the corresponding N-methoxy compound (generic name alachlor), the corresponding N-isopropyl compound (-crotch globaclor), and 3', 4'-dichloro 10 pionanilide (-pron9yl), P, dihalobenzonitrile herbicides, e.g. 2,6-dichloro-benzonitrile (-crop dichlobenyl), 3,5
-dibromo-4-hydroquinebenzonitrile (-ff name dibromoxynil and (j3. 5-short-4-hydroxybenzonitrile (common name ioxynil), Q, haloalkanoic acid herbicides, e.g. 2,2-nochlorobe) Robionic acid (-Je7),) iChloroacetic acid (common name TCA) and salts thereof, R, nophenyl ether herbicides, e.g. 4-nitrophenyl 2-nitro-4-) IJ full, r r+ Methyl/I/ phenyl ether (common name fluorocyphene), methyl J
-(214-dichlorophenoxy)-2-nitropenzoate (-crotch biphenox), 2-nitro-5-(
2-Chloro-4-(fluoromethylphenoxy)benzoic acid and 2-chloro-4-)IJ sololomethylphenyl 3-toxic 4-nitrophenyl ether, S,N-(heteroarylaminocal, ]? C1-N
-((4-Methoxy-6-methyl-1,3゜5-triazin-2-yl)aminocal7!so,ru]benzeneulphonabad ('general KDPX 4189 (!: known as T,N,N-nomethyldiphenol/architof'εt'' (common name nonenamide), N-(1-diphenod)
Tuculamine 1 (-crotch naphthalam) and 3-ami/-
1, 2, 4-1-reasy)"jf j2-mete, im
Weeding? jQ. Contact weeding for A1.
, Vivitritulium herbicide, for example, the active substance is 1°1'-
Herbicides that are trimethyl-4,4'-nobilizo1noium ion (-several people! lactate) and the active substance is 1,1'
- ethylene-2,2'-nobi1 no) 1 noum ion herbicides (-crotch diquate), ■, organic arsenic herbicides, such as mononato+7um methane alzenate (common name MSMA), and W, amino acid herbicides. agents such as N-(phosphonomethyl)-glycine (common name glyphosate) and its salts and esters. EXAMPLES Next, the present invention will be described in detail based on Examples 75; however, the present invention is not limited thereto. Example 1 Se(1) (1) 2.4% sodium chloride (15me) in acetone (IEILg) and water (15rne)
゜6-Dorimethoxybiliminone-5-CalJ? Stirred suspension of Kisyanogen (8g) ≦) JIJ Schiff'C
The mixture was stirred and refluxed for 4 hours, during which time a precipitate gradually formed. The suspension was diluted with water (100 mi!) and extracted with chloroform (2 x 100 mi!). Wash the organic layer with water and dry over magnesium sulfate. and the solvent was removed by evaporation under reduced pressure, ~1 point 98-99
1-(2°4.6-
Dorimethoxy5-pyrimidyl)butyl-1-ene-3
- Got on. (11), noether malonate (4,5 g,) was dissolved in sodium metal (0, f35) in absolute ethanol (30 m6).
1-(2,4,6-)dimethoxy-5-pyrimidyl)boudo-1-en-3-one (6,4 g) was added to the solution of , then boil the mixture for 2 hours. Potassium hydroxide water bath solution (3.5 g in 8 Qm/f water) was added and the mixture was heated to reflux for 5 hours. The solution was cooled and extracted with chloroform (5Qmg), then the aqueous layer was heated to 90°C and carefully acidified with dilute hydrochloric acid (Crtl 4.5 ). The formed precipitate was removed by filtration to a melting point of 215°C (
3-Hydroxy-5- as a pale yellow crystalline solid (decomposition)
(2,4,6-)liftoxy-5-bilimisol)cyclohexy-cun-1-one (5,2 g) was obtained. The p-liquid was extracted with ethyl acetate to obtain an additional 0.7 g of product. ) 3-Hydroxy-5-(2,4,6-)dimethoxy-5-pyrimidyl)cyclohexy-2-nin-1-one (1,4 g) f: dimethylformamide (1
0M) and to this solution was added sodium hydride (0.25 g of 601 dispersion in mineral oil). 11 of the solution
Heat to 0°C and after 15 minutes, zolopionic anhydride co,'
ime) was added with stirring. The mixture was stirred at 120° C. for 31121 hours, then the solvent was removed under reduced pressure. The residue was mixed with water (50 ml) and chloroform (2 x 50 mg).
) and the organic layer was dried over anhydrous magnesium sulfate and evaporated to give a brown color. Silica gel (60g
3-Hydroxy-5-(2,4,6-drimethoxy-5-pyrimidyl) was purified by column chromatography over (s eluent chloroform)
-2-propionylcyclohex-2-en-1-one (0.9 g, 56 units) was obtained. Proton magnetic resonance spectrum (cvct, : δ, pp
m) = 1.14 (3H, t); 2.3-4.0 (7H
. m ); 3.90 (9H, s ): 18.10 (Ill
, s). (7) 3-H)-0x-5-(2,4,6-drimethoxy-5-pyrimidyl)-2-zolopionylcyclohex-2-Xnor-1-one (1v) in 30 ml of absolute ethanol) Ethoxyamine hydrochloride (0.30 g) and then an aqueous sodium hydroxide solution (1 sg in 2 me of water) were added to a solution of ethoxyamine hydrochloride (0.90 g) with stirring at 20°C. After 20 hours at 20°C, the mixture was diluted with water (150#Ie
) and extracted with chloroform (2x, 75 min). The chloroporum layer was dried over anhydrous magnesium sulfate, and the solvent was removed by evaporation under reduced pressure to give 2-(1-(ethoxyε))f-rovir]-3-hydroxy-5-(2, 4,6-)dimethoxy-5-pyrimidyl)cyclohexy-2-r-7-1-one (900+
nC/) was obtained. The product was characterized by nuclear magnetic resonance spectrum analysis. Proton magnetic resonance spectrum (CDCl3: δ-ppm
) : 1.18(3■(,t ) :1.33(3
H, t): 2.2-4.0 (7H, m): 3.92 (9
H,s):4.10(2H,(1):]5.0(I
H, bs). Example 2, 3-hydroxy-5-(2,4,6-)dimethoxy-5-pyrimidyl)cyclohex-2-en-1-one [see (1) and (1) of Example 1], butyric anhydride (iii) and (1■) of Example 1 from the compound and ethoxyamine hydrochloride
It was prepared by essentially the same procedure as described in . The product was obtained as an almost colorless oil, which was characterized by nuclear magnetic resonance spectroscopy. Proton magnetic resonance spectrum (CDC63; δ-ppm
): 0.99 (3) 1. t): 1.31 (3H, t)
:1.55(2H2m):2.3-4.0'(7H,m
) * 3, 95 (9) I , s ) : 4.10 (
2H, q): 14.99 (IH, s). Shio 113 Nor-1-one (2) (i) Phosphorous oxychloride (51116,8g) was mixed with dichloroethane (40rnl) and dimethylformamide (10m
A solution of 4,6-simethoxy-2-methylthiobiliminone (6,7 g) in lX) was stirred at room temperature and then slowly added to kc
Added. The solution was boiled under reflux for 3 hours, then poured onto ice water and extracted with chloroform (2x6oaz).
o The chloroform extract was dried over magnesium sulfate, filtered and evaporated to give 4,6-dimethoxy-2-meprthiobiliminone-5 as a pale yellow solid with a melting point of 136°C.
-Carboxaldehyde (7 g, 95 parts) was obtained. (If) i-(4,6-simethoxy-2-methylthyme-5-biliminol)budo-1-en-3-one Y', 4+
6-Nonotokizo 2-methylthiopyrimidine-5-nonorpoxyalgahi 1'' was prepared by essentially the same procedure as described in Example 1 (1) and isolated as a pale yellow solid with a melting point of 112°C. . (iii) 3-Hydroxy-5-(4,6-dimethoxy'/-2-methylthio-5-pyrigodyl)cyclohexy-kun-1-one was converted to 1-(4,6-dimethoxy-2-methylthio -5-pyrimidyl)boudo-1-ene-
It was prepared from 3-one by essentially the same procedure as described in Example 1, 01) and was isolated as a creamy solid with a melting point of 195-200<0>C. (iv) 2-butyryl-3-hydroxy-5-[5
-(4,,6-Simethoxy-2-methylthio)]]Cyclohexy-2-2-1-o, 3-hydroxy-5-
(4,6-Simethoxy2-methylthio-5-pyrimidyl)cyclohex-2-en-1-one (Iiii
) and isolated as an orange oil. Proton magnetic resonance spectrum (CDC45; δ・ppm
)'0.98 (3H, t); 1.6'4 (2H, m)
;2.52(3H,s):2.5-3.7(7H,m
); 3.92 (6H, s): 18.0 (IH, bs). (φ 2-[1-(ethoxyimino)butylcou-3-hyProxy5-(4,6-simethoxy2-methylthio-5-pyrimidyl)cyclohex-2-en-1-one 4,2-butyryl-3- Hydroxy-5-, C5-(4
, 6-dimethoxy-2-methylthio)]] from cyclohex-2-en-1-o by essentially the same procedure as described in Example 1 (1 Proton magnetic resonance spectrum (CDCt5: δ, p voice): 0.98 (3I(, t): 1.31 (311, t)
; 1.6 (2H, m): 2.52 (3H, s): 2.4
-3.8 (7H, m): 3.92 (6) (', s: 4.
10(2H,q)", 15.0(IH, bs). Example 4 (i) From 2.4-dimethoxy-6-nomethylaminopyrimidine essentially as described in Example 3 (1) Using the same procedure, 2,4-dimethoxy-6-dimethylamino biriminone-5-carboxaldehyde was produced, with a melting point of 150
Isolated as a creamy solid at °C. (ii) From 2,4-dimethoxy-6-dimethylaminopyrimidine-5-carboxaldehyde, 1-(2,4-dimethoxy-6-dimethylaminopyrimidine-5-pyrimidine) was prepared by essentially the same procedure as described in Example 1. Zyl)budo 1-en-3-one was prepared and isolated as a pale cream colored solid with a melting point of 116°C. (111) Sodium (Noethyl Maloney) (2.8 g, 17 mmol) in ethanol (4 ome)
, 40 g, 17 mmol) were added to the bath solution and the solution was heated to reflux temperature. 1-(2,4-dimethoxy-
6-Nomethylavano-5-pyrimidyl)boudo-1-en-3-one (2.2 g, 9 mmol) was added and the mixture was then boiled at reflux for 2 hours. The ethanol was distilled off under reduced pressure and dimethylforma i The mixture was stirred and heated to 7JI] before adding n-butyric anhydride (2.9m/4). /f3'6
V- was heated at 120°C for 2 hours L2, then the solvent was removed under reduced pressure and hydroxylated) IJum aqueous solution (100M, 4
) was added. The aqueous mixture was washed for 4114 hours, then cooled and extracted with dichloromethane. The aqueous layer [ξ
(1) The mixture was heated to 60°C and neutralized with concentrated hydrochloric acid. Extraction with dichloromethane (2X 1.00 me) gave the crude product as a brown color. Purification by column chromatography on Norikaguru (nochloromethane as a filler) yields 2-butyryl-3-hydroxy-5-[5
-(2,4-diftquin-6-monomethylaminopyrimidyl)] to Sischif, quino-2-en-1-one (0,5 g
) was obtained as a colorless sample. 1 ton magnetic resonance spectrum (coct, : δ, p
pm): 0.9 o (3H' + t):
],, 6 (2H2m); 2.2-3.8 (7
H, m ): 3.09 (6H, n ); 3.84 (6H
, s): 18.20 (IH, s). (IV) 2-butyryl-3-hydroxy-5-[5
-(2,4-dimethoxy-6-nomethylaminopyrimidyl)]]cyclohexy-2-en-1-o of Example 1 (
1v) and this book'J (2-
[1-(ethoxyimino)butyl]-3-hydroxy-
5-(2,4-dimethoxy-6-monomethylaε)-5-
pyrimidyl)cyclohex-2-en-1-one was prepared and isolated as a brown color. Proton magnetic resonance spectrum (CDCl3: δ, ppm
): 0.98 (3H, t): 1.31 (3H, t):
1.6. (2H, m); 2.4-4.2 (9H, m):
3,,I 3(611,s) :3.88(6H,s
)': 10.9 (IH, bs). Example 5 (4) (+) a) Ethinoshi2,4,6-trimethylpyrimidine-5-carboxylate (H,,Og
Near Pan (Urban) &'/Unider (Shn)
ider), rlelv. Chjm, 8ctP, vol. 41, p. 1806 (1958)
] in anhydrous tetrahydrofuran (100 mg).
EJ L7) Ij was stirred with thiium aluminum hydride at room temperature for 2 hours. The solvent was completely evaporated and the residue was shaken with a few liters of water. The dried (Mg5O4) ethyl acetate extract was evaporated and the residue was purified by column chromatography on alumina and ethyl acetate for 8 hours to give 5-(hydroxymethyl)-, melting point 68°C.
2,4,6-trimethylpyrimidine was obtained as white crystals. h,) 5-(hydroxymethyl)-2,4,6-trimethylpyrimidine (5,0 g) and manganese diEAI (
35g)'<Heat under reflux for 8 hours in chloroform (200111g) with vigorous stirring. The mixture was filtered and the P solution was evaporated. The residue was chromatographed with m% dichloromethane through a short alumina column to give 2.4.6-)dimethylvirimicin-5-carboxaldehyde as white crystals that melted at 1°C of environment. Proton magnetic resonance spectrum (CDCl5: δ
-ppm): 2.71 (3Hs l1l):
2.78 (6H, s ); 10.65 (IH, s )
. c) 2.4.6-Trimethylpyrimicine-5-carboxaldehyde (1,4,1 and 1-triphenylphosphoranylidene-2-propane (1,'1 equim M) in toluene (150 mg) at 12 The solvent was evaporated and the residue was purified by column chromatography on silica del, eluting with ethyl acetate.
6-) Dimethylbilimicin-5-i/I/) Boudo 1-
En-3-one was obtained as an oil. Proton magnetic resonance spectrum (CDCl3: δ-pp
m): 2.41 (3H, s): 2.52 (6) 1. s
): 2.68 (3H, s): 6.44 (IH, d); 7
．． 62 (IH, d). (11) and oir+ 1-(2,4,6-trimethylpyrimidin-5-yl)budo-1-en-3-one (1,5L) and sodium diethylmalonate (2,
5 equivalents) was heated under reflux in absolute ethanol (4(IIA)) for 13 hours. Dilute aqueous potassium hydroxide solution (4 equivalents) f:
and the mixture was heated to distill off the ethanol over 4 hours. The hot solution was made just acidic by slowly adding dilute hydrochloric acid solution. Potassium bicarbonate (2 equiv h1) was added and the solvent was evaporated by vacuum distillation. The solid residue S was completely dried (1 (10°C, 0.1 mm Hg
) Residue/Ivt PA Anhydrous dimethylformamide C
4ome). The soluble fraction was heated at 100° C. with butyric anhydride (3 mg) under nitrogen gas for 2 hours. Nomethylform Lamide (40 ml) was evaporated by vacuum distillation and the residue was shaken with 1 i dilute acetic acid. The entire mixture was extracted with ethyl acetate. dry 11'k
(Mg504) Evaporate the solvent and leave 1? The product was purified by column chromatography on silica dal, eluting with ethyl acetate to give 3-hydroxy-5-(2,4
, 6-trimethylpyrimidin-5-.yl)-2-butyrylene chlorohex-2-en-1-one. Proton magnetic resonance spectrum (CDCl3; δ-pp
m): 1.0'1. (3H, t): 1.69 (2H,
m): 2.3-3.9 (7H, m): 2.57 (6H
,s):2.63(3H,g):18.33(IH,
g). (+v) 3-Hydroxy-5-(2,4,6-)rimetherbilibacyn-5-yl)-2-butyrylcyclohex-2-en-1-one (0.29 g) was dissolved in ethanol (30 mg). Among them, 〇-ethylhydroxylaine hydrochloride (o, zg) and sodium acetate trihydrate (0,'14
g) at room temperature for 15 hours. The mixture was poured into a saturated saline bath (50ml/l!') and then extracted with ethyl acetate. The dried (Na2S04) organic extract was evaporated to give 2-[:1-(ethoxyimino)butyl]
-3-Hydroxy-5-(2°4.6-drimethylbiliminon-5-yl)cyclohex-2-en-1-one was obtained as a colorless product. Proton magnetic resonance spectrum (CDCl5; δ-pp
m): 1.01 (3H, t): 1.34 (3H, t)
:ca 1.64 (2H, m) ;ca 2.3-3
．． 8 (7H, m): 2.59 (6H, s): 2.6
3 (3H1s): 4.13 (2) (, q'): 10.6
6(IFl,s). Example 6 Zyl-3-hydroxy-5-(5-4,6-dime1xy-2-methylthiopyriminol)]]cyclohexy2-
En-1-on 1+! I 3) and 3-chloroallyloxyamine hydrochloride were prepared by essentially the same procedure as described in 1. The product was produced as a nearly colorless oil. It was characterized by nuclear magnetic resonance spectroscopy. Proton magnetic resonance spectrum (CDC45: δ, ppm
): 0.97 (3'T(,t): 1.6
(2H1m) :”2.5-4.0’(7H,m):2
．． 53 (3H, s): 3.95 (GHr s)
; 4-4-4:, 8 (2T(+dofd);5.
9-6.4(,2H,m):15.0('II(,bs
). All 11 below 117 Dichloromethane (1 (3-picoline C40m in III)
9) and 2-(1-(ethoxyimino)butyl]-5-
(4,6-Simethoxy-2-methylf:t-5-hiIJminol)cyclohex-2-en-1-o” (2)
(8 omg) was stirred at room temperature and then treated with 3-trimethylacetyl chloride. After 2 hours, the solution was washed with dilute hydrochloric acid (IM, 20 mg), separated, dried over anhydrous magnesium sulfate, and evaporated under reduced pressure to give 3-trimethylacetyloxy-2-C1-(ethoxyimino).
Butyl]-5-(4,6-simethoxy2-methylthio-5-biriminol)cyclohex-2-en-1-one (7) was obtained as 1,0 (u9) by nuclear magnetic resonance analysis. Characterized by proton magnetic resonance spectral analysis (CDCl3: δ-ppm
-il'): 0.99 (311, t): 1.27 (9H
,s):1.32(3H,t);1.6(2H-η)S
2.4-3.8 (7H, m): 2.53 (3H, s)
;3.95(64(,s) ;4.12(2B, q
). Example 8 Thorium hydroxide (10 m
g) Nota M in methanol (2(1/)
41-(ethoxyi))butylcou-3-hydroxy-
5(2,4,6-drimethoxy5-pyrimidyl)cyclohex-2-en-1-one (!5) (60#l)
was added to the solution. The solvent was removed under reduced pressure to give the title compound a pale brown 161 substance (6(1&
) was obtained. 119 This Example 1 shows 1Jt! of the 1,000-substituted pyridine-5-carboxaldehyde of the general formula (■) used in the preparation of the compounds of the present invention. ! 4) Explains the manufacturing method. (i) (2-[(trimethylamino)methylene]p)
pn) i'den)bis[dimethylammonium g-chlorate] was prepared by Arnold's method [Co11ect].
. Czech, Chem, Comm, Volume 30, 212
5 (1965)] by formylation of bromoacetic acid. (11) tsil/F in methanol (200 mg)
-ri. rate salt (+4.8 g) and acetaminone hydrochloride (4
, 0g) of 1-(1,Qfi) solution was finger pressed at 40°C while gradually adding a solution of 1-(1,Qfi) in methanol (5Qm/ml). After 3 hours, the solution was diluted with acetic acid. The residue was diluted with water (5Q+n(.) and extracted with chloroform (,2xloOmN). The chloroform extract was dried and evaporated to give 2-methyl bicarbonate
Limidine-5-kalajfgishialdehyde (2.5g,
49%). The product was characterized by proton nuclear magnetic resonance shelving analysis, and the shedding was determined by the second
IBa on the table. Seven no f cold 4p/ of the general formula (V) shown in the second column below
l pyrimidine-5-carboxaldehyde, +2-
[(Dimethylamino)methylene] Zorono? 2-Methylpyrimidine-5-
SP! by the procedure described for the construction of carboxyalpine The produced O product was determined by the proton G (gas resonance) by kutor analysis, and the spectrum was recorded in the second thorn below. -(1-(Ethoxyimino)butylcou-3-hydroxy-5-(2-methyl-5-pyrimidyl)cyclohex-2-en-1-one (9) (1) Acer-7 (5(I
2-methylpyrimidine- in I/) and water <30me)
A bath solution of 5-carboxaldehyde (4 g) was poured into a sodium hydroxide water bath (1 (2%, 5
'ml! ). The solution was incubated overnight at room temperature.
M'i (, then concentrated under reduced pressure and diluted tAl l":
It was neutralized in one shot. The mixture φ was extracted with oil, dried over anhydrous magnesium sulfate, and evaporated under reduced pressure to give 1-[5-(2-methylpyrimidyl)budo-1-ene-] as a light brown color.
3-one (2,3,V, 43) (r- obtained.
6p) and the bath liquid was heated to reflux. 1-
[5-(2-methylpyrimidyl)but-1-ene-3-
Men (2,3,'/) was added and the mixture was heated briefly for 2 hours. Sodium hydroxide bath solution (2 in 30ml of water)
．． 0 g) was added and the solution was refluxed for a further 5 hours. ! η,
((lj was acidified to pH 4 with agricultural hydrochloric acid and carbon dioxide slurry), then made alkaline by adding sodium bicarbonate. The bath solution was evaporated to dryness and the melting point was 200°C.
3-Hydroxy-5-[(
2-Methylpyrimidyl)]]Sodium salt of cyclohexy-2-en-1-o (2,3,?, 72) was obtained. ψ1) 3-Hydroxy-5-(5-(2-methylpyrimidyl))]cyclo\xy-2-en-1-o sodium salt (2,0,?) was stirred at 9.0°C, Formamide (dissolved in 1 (1/?). Butyric anhydride C1,4me) was added to this solution and heating was continued for 1 hour at 110°C. The trimethylformamide was evaporated under reduced pressure and the residue was dissolved in water ( 2omB and ooborum (,
'40 mg). The chloroborum layer was separated, dried over anhydrous magnesium sulfate, evaporated and the resulting oil was purified by column chromatography on silica gel (eluent chloroform) to give 2-butyryl-3-hydroxy-5-45. -(2-methylpyrimidyl)]]cyclohexy2-:L7-1-one (8
Q Q mg, 30%)? I asked why. (1■) Ethanol (2-butyryl-3- in 5 oml)
Hydroquine-5-[5-(2-methylpyrimidyl)]
Dichlorohex-2-en-1-one 6001〃9:
2.2 mmol)ノ/￥/l'f, in chamber 6n;
i Ethoxyamine hydrochloride (240 In?, 2
．． 5 mmol) and then sodium hydroxide (1 (10 mg)) in water (1 mg) were added. After 20 hours, the ethanol was removed by evaporation in vacuum F. 2-[1-(ethoxyimino)butyl)-3-hydroxy-5 -[5-(2-methylpyrimidyl)]]cyclohexy-2-2-one 600 rin
87) was obtained. The proboscis and each intermediate 1 and 1 (produced by broton nuclear magnetism (1
Characterized by Lis vector analysis, the spectra of intermediates and final products were identified as I+U19, 20 and 21 of 4.
3 taste, +', l, 42% andhi6i't 5 a
K nlL Ek 'i-le. 9
1110 (1) to (1). the products and intermediates are each characterized by proton nuclear magnetic resonance spectroscopy;
The spectra of the intermediates and final products are recorded in Examples 19, 20 and 21, Coating 3, Table 4 and Coating 5. 1J12 (1) to (1) of Example IO, except using propionic anhydride in (lii) instead of gold, butyric anhydride
) was prepared by the same operation 1' as described in J4. The product and intermediate were analyzed by proton nuclear magnetic resonance spectroscopy.
Characterize the spectra by Examples 20 and 210
Record the results in Table 4 and Approximately 57 minutes. Example 13 2-[1-(Ethoxyimino)propyl-3-(13) 2-(1-(Ethoxyimino)F90]-3-hydroxy-5-(5) -(2-
Methylthiopyrimidyl)]]cyclohexy-2-en-1-one (180 my) in water rI sodium chloride solution (1.0 m in methanol 5 Qm/!)
1.1 g of solution) was added. The solution was evaporated under reduced pressure to give 2-[1-(ethoxyimino)norobyl]-3-hydroquine-5-[5-(2-methylthiopyrimidyl)]]dichlorohex-2-ene-1-
The sodium salt (13) of E was obtained as a light colored box with a melting point higher than 200°C. 2-[1-(ztoxy-(mino)propyl-3-hydroxy-5-C5-) in dichloromethane (10 m/4)
C2-methylthiopyrimidyl)]]cyclohexy2-
A solution of 3-chloroperbenzoic acid (40%) in dichloromethane (3(Ilg)) was prepared at 5°C.
0111g) in bath i3't. The solution was warmed to room temperature and left for 24 hours. The solvent was removed under reduced pressure and the residue was purified by column chromatography on silica gel (eluent chloroform) to give 2-[1-(
ethoxyimino)propylcou-3-hydroxy-5-(
5-(2-methylsulfinyl bilibadyl)]]cyclohexy-2-en-1-one 1.4) (30C19,4
6) was obtained as a nearly colorless solid. The product was characterized by proton magnetic resonance spectroscopy and the spectra are reported in Table 5 of Example 21. Example 15 (15) units, 2-butyryl-3-hydroxy-5 (5
-(2-Methylthiopyrimidyl)] to shishif=vfushi-
-en-1-one and 3-chloroallyloxyamine in a similar procedure to that described in Example 10 (1v). The product is characterized by proton magnetic resonance spectroscopy and the spectrum is recorded in Example 21, number 57'L. 1-16-one (16) trimebul acetyl chloride (0,10, 16-one)
2-[1-(ethoxyimino)butylio3-hydroxy-5-[l5-
(2-Methoxypyribasyl)]]Cyclohequin-2-en-1-one 11) (0,151 and 3-picoline (added to a solution of 0,10,1 with 43 i 'r') at room temperature. After 2 hours, the solution was diluted with dilute hydrochloric acid (LM,
1. separated, dried over anhydrous magnesium sulfate and evaporated under reduced pressure to give 3-trimethylacetyloxy-2-('l-(ethoxyimino)butyl)-
5-[:5-(2-methoxypyriminol)]]cyclohexy-2-ene-1-one 16) without a battery (15omy
) was obtained. The product was characterized by proton magnetic resonance spectroscopy and the spectra were recorded in Table 5 of Example 21. During the purification of 5-(2-methylthiopyrimidyl)]cyclohexy-2-en-1-one (12), it was chromatographically purified. 7
It is believed that the trimethylamino group was introduced during the acylation step [Part 10, (111)]. The compound was characterized by proton nuclear magnetic resonance spectroscopy and the spectra are shown in Table 5 of Example 21. The same procedure as described by Klm and Mc Kee [J, Org, Chem, Vol. 35, 455
(1970)] to prepare 2-hydroxy-7mer-5=methylpyrison. Proton magnetic resonance spectrum (CDC/-3: at δ-ppm):
2.32 (3H.s): 3.6 (III, bs): 4.80 (2H1
(it) 2-hydroxymethyl-5-methylpyrimidine to 5-methylpyrimidine-2-carboxaldehyde by oxidation with excess manganese dioxide in chloroform. The product was obtained as colorless crystals, which were characterized by noroton nuclear magnetic resonance spectroscopy (cDct3; δ-pp
m): 2.44 (3H, s): 8.80 (2H, s)
:10.06 (IH+s). G11) From 5-methylpyrimidine-2-carboxaldehyde, 2-(1-(ethoxyimino)f-ropyl)- by essentially the same procedure as described in Example 1o (1) to (iV) 3-hydroxy-5-[2-(5-
methylpyrimidyl)]]cyclohexy'2-ene-1
-one 18) was produced. Each intermediate and product was characterized by proton nuclear magnetic resonance spectroscopy and reported in Tables 3, 4 and 5 of Examples 19, 2o and 21.
Record in table. Below is white. Example 19 General formula (Via
) of 1-(mono-substituted pyrimidyl)budo-1-ene-3
-one was characterized by proton nuclear magnetic resonance (p m r ) spectroscopy. For convenience, the pmr data is recorded in Table 3 below. Table 3 Example 2〇 General formula (Xl[
) was characterized by 2-acyl-5-(mono-substituted pyrimidyl)cyclohexane-1,3-dione all-proton nuclear magnetic resonance spectroscopy. For convenience, the pmr data is recorded in Table 4 below. Most compounds are obtained as oils or low melting solids,
It was generally colorless or light brown. Table 4 Example 21 The tηIS portion of the mono-substituted pyrimidyl compound of the present invention was obtained as a colorless or light brown oil or a low melting solid. These can be characterized and identified by nuclear magnetic resonance spectroscopy. For convenience, the nuclear magnetic resonance spectrum (pmr) data is shown below at 4゛ゞ''''81-°
1122 This example describes the production of formulations of compounds of the invention.
11. However, the present invention is not limited to this.
e, 6: a) Emulsifying compound '4'1lAi k 7%φ
ic) "N13 and 3 v/v" Kenmad (Kem
mat)" S C15B 'f6 is dissolved in toluene containing emulsifiable concentrate 1). This emulsifiable concentrate 1 is an aqueous solution that can be diluted with water to the desired degree and sprayed. It can be made into an emulsion.
'J 13 is ethoxylation of nonylphenol/:1=
It's a D'i thing. “Kummatopa is the quotient (“seven power”), “rimanmato” SC
] 5B is a combination of dodecylbenzene sulfone acetic acid calcium jp7r. ) b) Water + IHii), j, hot liquid combination! 1・≧'1&1 (5'fQ foot) and °°Dyapol ” P T (11jFi
'jpl; ) t Add it to the water solution (94 weight, jet part) of "Derik" N8, and mix the mixture with ha? - Lumilling to produce a stable aqueous suspension. This suspension can be diluted with water to the required consistency to produce an aqueous suspension that can be applied by spraying. (゛Dia,]5-L'' is the old I mark, and ``Diapol'' PT is an anionic/f-ionic clouding agent. ) C) Emulsifying hydrocarbon compound 1 (10% parts by weight)
i Raf R11) and "Kenmado" SC], 5
B (5n: 8 copies) * “Solve
sso) ” 150 (80 small pi part) K melt t!i!
Is it emulsifying? You can make "F thick material". This is diluted with water at once and sprayed with h11
You can make a water bottle for 1i. ('°Tsurupets' is a trademark, and 'Tsurupets' 150 has a high-boiling aroma of S petroleum distillate.) d) Dispersible powder compound JK+, 1 (10 stacked parts), 'Madexyl (
4atexil) ” DA/AC (triple fr+F
r1s), “Aerosol”
(') T/B (l gi Jij part) and Clay 298 (8G ilj, '>it part) were thoroughly mixed and then milled to obtain a powder composition with a grain size of less than 50 microns. (゛′Machixil” is a trademark, °゛Machixil″1
A, /ACi, +: naphthalene sulfone with formaldehyde (,1 natural 1 disodium) 11λ
It is. ``Chi 1'-Rosol'' is a commercial stopper, and ``Aerotsuru'' OT/B is the octyl ester of sodium sulfosuccinate! It is a 17' sword. ) e) Height "1 degree i1, "・1 thick compound j); 1 (99 ton F? part), silica knee location 8 ru (05 in r, part) and self-contained, p7jF % ton f (
j; Shiri: /J ((1,57j f11 parts) was combined and ground in a shimmer mill to produce a powder smaller than 20 (1 micron). f) (11 powder cutting compound! 13/lA 1 (10Alj 4r;'FiB
), -rtanogurgite (IQ 7H7l-i parts) and 1 stone (80 parts)) and then ground in a no shimmer mill to form particles smaller than 200 microns. Paddy rice with small larvae was produced. What is the emulsifying property of the compound of the present invention? , 1υ
The liquid was placed on parts a), b) and 1tc), and then mixed in a woody manner, and then added with a surfactant and/or oil. diluted with water containing water to the required concentration to make composition 1, which was added to the germination n11 and post-germination removal agent of compound 11 as described in 123 and 24. tzu1123 (T!l 22 to 8r: ffJ (pre-germination% of the compound of the present invention, j', 7f)
The following 7 works made it worth it. Test j'ji, :,3 nl-F was sown in rows at a depth of 2 (,11z.1
) is a cotyledon and a cotyledon! Hit + in separate oil! 1t + l, , 幡fi + confront (, 2 boxes were sprayed with #11 product l of the invention. The two boxes with diffraction were trained in the same way, but Group f of the present invention
i, Q, %+na: Streak 1/- width, for comparison purposes ('J
・Used. Place all boxes in a room and water lightly by spraying from above to initiate germination, then bathe under flH for 3 weeks as required for optimal plant growth. , 11 boxes were taken out from the hot and cold room and placed in the
The effectiveness was evaluated visually. Results'ff: Shown in Table 6, the table also includes the evaluation of 4'J4 damage on plants on a scale of 0 to 5.
0 indicates damage to units 0 to 10, 1 indicates damage to units 11 to 30, 2 indicates damage to units 31 to 60q4, and 3 indicates damage to units 6 to 60.
1 to 80 stages of bruises are shown, 4i: 81 to 99 stages of tree damage are shown, and 5 parts of 100 stages are withered. Dash (-) is 1
Indicates that no experiment was conducted. The names of the plants tested are as follows: wh
Wheat Ot Machite's oats Rg Honmugi Jm Japanese barnyard grass P Entou Ip Aza ga O + V Ri S Mustard Sf Sunflower All white Table 6 Example 24 The post-emergence herbicidal action of the compound of the present invention formulated as described in Example 22 Evaluation was performed by the following operation. 2c77 in Wanganchu who put the miko to be tested in a glaze box? The seeds were sown in rows at a depth of . 11"L cotyledonous and dicotyledonous seeds were sown in two separate boxes. The four boxes were placed in the greenhouse and lightly watered by top spray to initiate germination, then optimally τt1! was carried out underground as necessary to grow the plants.If the material was about 10 to 12.5
After growing to a height of 1177z, one box each of cotyledons and dicots was removed from the greenhouse;
The entire core element was sprayed with the composition of the present invention. After spraying, the boxes were returned to the greenhouse for a further 3 weeks [141] and the effect of the treatment was evaluated by comparing meat 1 to untreated controls. The results are shown in Table 7; 0 damage to 1 object
Measured on a scale of ~5, 0 indicates 04 scratches from 0 to 10 inches, 1 indicates damage from 11 to 30 degrees, 2 indicates +('i scratches from 31 to 60 degrees, and 3 f =1.'61~80ch]
D Jin,'! 1ll-indicates, 4 is 4'ii of section 81-99
Ot, %, 1.5 indicates 100 dead gold. Darashi (-)kl:s indicates that the experiment was not performed. The name and profit of 胛ち41/l 'l;+-: is as follows:■ Wheat Ot 'R's Auto Dai 1? , g Honmugi Jm Japanese barnyard grass P Entou Ip Azaga MS Mustard Sf Sunflower Table 7 Example 25 21.9 fl/(l of "Span" 80 and 7B, !/l ° in methylcyclohexanone
“Tween” 20 f bath solution containing 16 o
Compounds were formulated for testing by thoroughly mixing with emulsion 5me prepared by diluting to 500ml with mt;q water. °゛Span 80
tj, superficially active rhinoceros 1 sub-i containing sorbicun monolaurate! l, 'I'm going to do two things. ``Tween'' 2Qi11 is a trademark of the Table i'?+j activator containing a condensate of sorbitan monooleate and 20 moles of ethylene oxide.
4 ml of each emulsion containing the compound with water
0m1. diluted with the seeds listed in Table 8 below, 6+-, 9]
Sude I/- was applied on young plants of J. 1
After 4 days, a 1-incision wound on the mixed 1-in Li material was made with a diameter of 0 to 5 mm.
0 indicates a loss of 0 to 20 inches, and 5 indicates complete death. In order to test the germination effect of HIT, fi7 offspring of the mixed plants were placed in shallow grooves formed on the soil gripping surface of the tray.Next,
Flatten the surface, spray, and roughen ± g (', ', 5
Spread evenly over ten of the sprayed surfaces. Herbicidal action
Price? ! - After 21 days, the degree of damage caused by weeding was compared to the untreated vs. 1: (Assessed by comparison with the product. The results are shown in the 8th column of the lower Be. Darashi (-) indicates that no rebellion was carried out. The names of the test items are as follows. Chi-Ri deru: sb
Ranna Rp Western rape Ct Zan 1 sy Soybean haku z Corn Ww Autumn wheat nc Rice (Ipomea 1+urpurea) m (Amuranthus retroflexus) P
i Poly
perus rotundus) rear (AU) ■PF
9406 0 Inventor Graeme John Farquharson 10 Reservoir Steane Street, 30 73 Victoria, Australia

Claims (1)

[Claims] 1. General formula (I): [In the formula, X is the same or different and each independently represents a halogen; a nitro group; a cyano group; an alkyl group having 1 to 6 carbon atoms; a halogen , a nitro group, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, and an alkylthio group having 1 to 6 carbon atoms substituted with a substituent selected from the group consisting of Group; number of carbon atoms: 2~
6 alkenyl groups; alkynyl groups having 2 to 6 carbon atoms; Hydroxy group; alkoxy group having 1 to 6 carbon atoms; alkoxy group having 1 to 6 carbon atoms substituted with a substituent selected from halogen and alkoxy group having 1 to 6 carbon atoms; carbon atom 2 to 6 alkenyloxy groups;
Alkynyloxy group having 2 to 6 carbon atoms; Alkanoyloxy group having 2 to 6 carbon atoms; 1 to 1 to alkoxy group
Alkoxycarbonyl group having 6 carbon atoms; alkylthio group having 1 to 6 carbon atoms; alkylsulfinyl group having 1 to 6 carbon atoms; alkylsulfonyl group having 1 to 6 carbon atoms; sulfamoyl group; alkyl based on 1
N-alkylsulfamoyl group with ~6 carbon atoms; N,N with 1 to 6 carbon atoms in each alkyl group
-Dialkylsulfamoyl group; penzyl-o'Y'i
Group: Hensen ring halogen, nitro group, number of carbon atoms: 1
a group substituted with 1 to 3 substituents selected from the group consisting of ~6 alkyl groups, alkoxy groups having 1 to 6 carbon atoms, and haloalkyl groups having 1 to 6 carbon atoms,
Substituted benzyloxy group: group NR5B' (in the formula R5 and R6
each independently selected from the group consisting of hydrogen, alkyl groups having 1 to 6 carbon atoms, alkanoyl groups having 2 to 6 carbon atoms, benzoyl groups and benzyl groups); formyl groups and 2 to 6 carbon atoms; 6 alkanoyl groups and their oxime, imine and Schiff base derivatives; R1 is hydrogen; alkyl groups having 1 to 6 carbon atoms; alkenyl groups having 2 to 6 carbon atoms; ; Alkynyl group having 2 to 6 carbon atoms; alkoxy group having 1 to 6 carbon atoms, alkylthio group having 1 to 6 carbon atoms, phenyl group and substituted phenyl group (pentene ring carhalogen, nitro group); , cyano group, number of carbon atoms 1~
6 alkyl groups, haloalkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and alkylthio groups having 1 to 6 carbon atoms; Substituted alkyl group with 1 to 6 carbon atoms substituted with a substituent consisting of 3 substituents: Alkylsulfonyl group with 1 to 6 carbon atoms: Benzene sulfonyl group: Benzene ring, halogen, nitro group, cyan group, alkyl group having 1 to 6 carbon atoms, 1 to 6 carbon atoms
a substituted benzenesulfonyl group substituted with 1 to 3 substituents selected from the group consisting of 6 haloalkyl groups, alkoxy groups having 1 to 6 carbon atoms, and alkylthio groups having 1 to 6 carbon atoms; ; acyl group; and an inorganic or organic cation; R2 is an alkyl group having 1 to 6 carbon atoms; 2 carbon atoms;
~6 alkenyl groups; haloalkenyl groups having 2 to 6 carbon atoms; alkynyl groups having 2 to 6 carbon atoms; haloalkynyl groups having 2 to 6 carbon atoms; and alkyl groups in which the alkyl group is a halogen or a carbon atom Alkoxy group with 1 to 6 carbon atoms, alkylthio group with 1 to 6 carbon atoms, phenyl group and hbenzene ring are halogen, nitro group, cyano group, 1 to 6 carbon atoms
argyl group having 1 to 6 carbon atoms, haloalkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, and 1 carbon atom
1 to 6 carbon atoms substituted with a substituent selected from the group consisting of a substituted phenyl group substituted with 1 to 3 substituents selected from the group consisting of ~6 alkylthio groups
substituted alkyl groups, R3 is an alkyl group of 1 to 6 carbon atoms,
~6 fluoroalkyl groups, alkenyl groups having 2 to 6 carbon atoms, alkynyl groups having 2 to 6 carbon atoms, and phenyl groups, R4 is hydrogen, halogen, cyano group, carbon atom 9 selected from the group consisting of 1 to 6 alkyl groups and alkoxycarbonyl groups having 1 to 6 carbon atoms in the alkoxy group, and n represents an integer of 1 to 3. 2. X is the same or different, and each independently represents a halogen; a nitro group; a cyano group; an alkyl group having 1 to 6 carbon atoms; a halogen, a nitro group, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms; and an alkyl group having 1 to 6 carbon atoms substituted with a substituent selected from the group consisting of an alkylthio group having 1 to 6 carbon atoms: an alkyl group having 2 to 6 carbon atoms.
alkenyl group: alkynyl group having 2 to 6 carbon atoms: hydroxy group; alkoxy group having 1 to 6 carbon atoms;
An alkoxy group having 1 to 6 carbon atoms substituted with a substituent selected from halogen and an alkoxy group having 1 to 6 carbon atoms; an alkenyloxy group having 2 to 6 carbon atoms:
Alkynyloxy group having 2 to 6 carbon atoms; Alkanoyloxy group having 2 to 6 carbon atoms: 1 to 1 to alkoxy group
Alkoxycarbonyl group having 6 carbon atoms; alkylthio group having 1 to 6 carbon atoms; alkylsulfinyl group having 1 to 6 carbon atoms; alkylsulfonyl group having 1 to 6 carbon atoms; sulfamoyl group: alkyl based on 1
N-alkylsulfamoyl group with ~6 carbon atoms; N,N with 1 to 6 carbon atoms in each alkyl group
-Dialkylsulfamoyl group; hensyloxy group; benzene ring carhalogen, 0 nitro group, alkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, and haloalkyl group having 1 to 6 carbon atoms a substituted benzyloxy group substituted with 1 to 3 substituents selected from the group consisting of; a group NR5R6 (wherein R5 and R6 are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, a carbon and formula -C(R
7) =NR8 (wherein R7 is selected from hydrogen and a nyl group, a benzyl group, a hydroxy group, a carbon XeJJ! 11 to 6 alkoxy groups, a phenoxy group and a benzyloxy group) and R1 is hydrogen: an alkyl group having 1 to 6 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; 1 having 2 to 6 carbon atoms
-Vnyl group; alkoxy group where the alkyl group has 1 to 6 carbon atoms, argylthio group with -6 carbon atoms, phenyl group and substituted Jenyl group (where the benzene ring is H1 cogen,
Nitro group, cyan group, alkyl group having 1 to 6 carbon atoms, haloalkini group having 1 to 6 carbon atoms, carbon atom T-
1 to 3 substituents selected from the group consisting of alkoxy groups having 1 to 6 carbon atoms and alkylthio groups having 1 to 6 carbon atoms;
Substituted alkyl group having 1 to 6 carbon atoms, substituted with a substituent consisting of
6 alkylsulfonyl groups; benzenesulfonyl group;
The benzene ring is a halogen, a nitro group, a cyan group, an alkyl group having 1 to 6 carbon atoms, a no-roalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a carbon atom number A substituted benzenesulfonyl group substituted with 1 to 3 substituents selected from the group consisting of 1 to 6 alkylthio groups; an alkanoyl group having 2 to 6 carbon atoms; a benzoyl group; , nitro group,
From the group consisting of a cyan group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alkylthio group having 1 to 6 carbon atoms. Substituted benzoyl group substituted with 1 to 3 selected substituents; 2-furoyl group; 3-furoyl group; 2-thenoyl group; 3-teno-fl group; and alkali metal ion, alkaline earth Gold L ion, migrated metal ion and ammonium ion R9R10R11R1,2N■
(In the formula, R9, n10, R11 and R12 are each independently hydrogen; an alkyl group having 1 to 10 carbon atoms; the alkyl group is from the group consisting of a hydroxy group, halogen, and an alkoxy group having 1 to 6 carbon atoms) A substituted alkyl group having 1 to 10 carbon atoms substituted with a selected substituent; a phenyl group; a benzyl group; and a benzene ring having a halogen, a nitro group, a cyan group, an alkyl group having 1 to 6 carbon atoms, Haloalkyl group having 1 to 6 carbon atoms, 1 to 6 carbon atoms
(selected from the group consisting of a substituted phenyl group and a substituted benzyl group) substituted with one to three substituents selected from the group consisting of alkoxy groups and alkylthio groups having 1 to 6 carbon atoms. selected from the group consisting of selected inorganic or organic cations, and R2 has 1 to 6 carbon atoms;
an alkyl group; an alkenyl group having 2 to 6 carbon atoms;
Haloalkenyl group having 2 to 6 carbon atoms; 2 carbon atoms
~6 alkynyl groups; haloalkynyl groups having 2 to 6 carbon atoms; and alkyl groups having halogen and 1 to 6 carbon atoms;
6 alkoxy groups, alkylthio groups with 1 to 6 carbon atoms, phenyl groups, and benzene rings with halogens, nitro groups, cyan groups, alkyl groups with 1 to 6 carbon atoms, and 1 to 6 carbon atoms. from the group consisting of substituted phenyl groups substituted with 1 to 3 substituents selected from the group consisting of haloalkyl groups, alkoxy groups having 1 to 6 carbon atoms, and alkylthio groups having 1 to 6 carbon atoms; selected from the group consisting of a substituted alkyl group having 1 to 6 carbon atoms substituted with a selected substituent, and R3 is an alkyl group having 1 to 6 carbon atoms, 1 carbon atom;
~6 fluoroalkyl groups, alkenyl groups having 2 to 6 carbon atoms, alkynyl groups having 2 to 6 carbon atoms, and phenyl groups, R4 is hydrogen, halogen, cyan group, carbon atom 1 to 6 alkyl groups and alkoxycarbonyl groups having 1 to 6 carbon atoms in the alkoxy group, and n represents an integer of 1 to 3. Compound. 3. X is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, a norogen, or a haloalkyl group having 1 to 6 carbon atoms. R1 is hydrogen; carbon atom Alkyl group having 1 to 6 carbon atoms; alkenyl group having 2 to 6 carbon atoms; alkynyl group having 2 to 6 carbon atoms: alkoxy group in which the alkyl group has 1 to 6 carbon atoms, number of carbon atoms 1 to 6 alkylthio groups, phenyl groups and substituted phenyl groups (benzene ring is a halogen, nitro group, cyano group, argyl group having 1 to 6 carbon atoms,
1 to 3 substituents selected from the group consisting of a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alkylthio group having 1 to 6 carbon atoms; 1~. Substituted alkyl group having 1 to 6 carbon atoms, substituted with a substituent selected from the group consisting of Rings include halogen, nitro group, cyano group, alkyl group having 1 to 6 carbon atoms, haloalkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, and 1 to 6 carbon atoms Substituted pe/zenesulfonyl group substituted with 1 to 3 substituents selected from the group consisting of alkylthio groups; Alkanoyl group having 2 to 6 carbon atoms; Benzoyl group: benzene ring is halogen, nitro group , a cyano group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, and an alkylthio group having 1 to 6 carbon atoms. a substituted 4-enzoyl group substituted with 1 to 3 substituents selected from the group; 2-furoyl group;
3-furoyl group; 2-thenoyl group; 3-thenoyl group;
and alkali metal ions, alkaline earth metal ions, transition metal ions and ammonium ions R9R10Et1
1R 12 Substituted alkyl groups having 1 to 10 carbon atoms substituted with selected substituents: phenyl group; benzyl group; and benzene ring)
rogene, nitro group, cyano group, alkyl group having 1 to 6 carbon atoms, no-roalkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, and 1 to 6 carbon atoms
an inorganic or organic radical selected from the group consisting of substituted phenyl groups substituted with 1 to 3 substituents selected from the group consisting of alkylthio groups; selected from the group consisting of ions, where R2 is an alkyl group having 1 to 6 carbon atoms: 2 carbon atoms;
~6 alkenyl groups; haloalkenyl groups having 2 to 6 carbon atoms; alkynyl groups having 2 to 6 carbon atoms; no-loalkynyl groups having 2 to 6 carbon atoms; , alkoxy groups with 1 to 6 carbon atoms, alkylthio groups with 1 to 6 carbon atoms, phenyl groups and benzene rings, nitro groups, cyan groups, alkyl groups with 1 to 6 carbon atoms , 1 to 3 substituents selected from the group consisting of a no-roalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alkylthio group having 1 to 6 carbon atoms; selected from the group consisting of substituted alkyl groups having 1 to 6 carbon atoms substituted with a substituent selected from the group consisting of substituted phenyl groups, and R3 is an alkyl group having 1 to 6 carbon atoms; , number of carbon atoms: 1
selected from the group consisting of ~6 fluoroalkyl groups, alkenyl groups having 2 to 6 carbon atoms, alkynyl groups having 2 to 6 carbon atoms, and phenyl groups, R4 is hydrogen, and n is 1 to 3. A compound according to claim 1 or 2 selected from an integer of 3. 4. X is each independently an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, or an alkylsulfinyl group having 1 to 6 carbon atoms. group, alkylsulfonyl group having 1 to 6 carbon atoms, halogen, amino group, alkyl group with 1 to
selected from the group consisting of N-alkylamino groups having 6 carbon atoms and N,N-di(alkyl)amine groups having 1 to 6 carbon atoms in each alkyl group, R1 is hydrogen; a carbon atom Several 2 to 6 alkanoyl groups; pensoyl group and hibenzene i are norogen, nitro group,
To an alkyl group having 1 to 6 carbon atoms and 1 carbon atom,
F-substituted benzoyl group substituted with 1 to 3 substituents selected from the group consisting of 6 alkoxy groups; benzenesulfonyl group; 1 to 3 of the substituents selected from the group consisting of alkyl groups and alkoxy groups having 1 to 6 carbon atoms;
Substituted benzenesulfonyl groups substituted with
(argyl) from the group consisting of inorganic or organic cations selected from ammonium ions, where the alkyl group is selected from alkyl groups of 1 to 6 carbon atoms and hydroxyalkyl groups of 1 to 6 carbon atoms; selected, R2 is an alkyl group having 1 to 6 carbon atoms, 2 carbon atoms
~6 alkenyl groups, alkynyl groups having 2 to 6 carbon atoms, haloalkyl groups having 1 to 6 carbon atoms, haloalkenyl groups having 2 to 6 carbon atoms, and halo groups having 2 to 6 carbon atoms alkynyl groups, R3 is selected from alkyl groups having 1 to 6 carbon atoms, R4 is selected from hydrogen and halogen, and n is 1 to 6;
3. A compound according to claim 1 or 2, wherein the compound is an integer selected from 3. 5. General formula (IID: [In the formula, each X is independently an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an argylthio group having 1 to 6 carbon atoms, a carbon atom Alkylsulfinyl group having 1 to 6 carbon atoms, halogen, amino group, alkyl group having 1 to 6 carbon atoms
selected from the group consisting of N-alkylamino groups having 1 to 6 carbon atoms and N,N-di(alkyl)amine groups having 1 to 6 carbon atoms in each alkyl group; R1 is hydrogen; ~6 alkanoyl groups, benzoyl groups, alkali metal ions, transition metal ions,
Ammonium ion and tri- and tetra-(alkyl)ammonium ion (alkyl group has 1 to 6 carbon atoms)
alkyl groups having 1 to 6 carbon atoms and hydroxyalkyl groups having 1 to 6 carbon atoms), and R2 is an alkyl group having 1 to 3 carbon atoms;
-3 selected from the group consisting of haloalkyl, allyl and no-loallyl, R3 is selected from alkyl groups of 1 to 3 carbon atoms, R4 is hydrogen, and n is from 1 to 3 is a selected integer]; 6. X is each independently an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, and 1 to 6 for each alkyl group;
selected from the group consisting of N,N-di(alkyl)amino groups having 6 carbon atoms, R1 being hydrogen, carbonite number 2
~6 alkanoyl groups and alkali metal ions, R2 is selected from the group consisting of alkyl groups of 1 to 3 carbon atoms, allyl groups and haloallyl groups, and R3 is selected from the group of 1 to 3 carbon atoms; 6. A compound according to any one of claims 1 to 5, selected from three alkyl groups, R4 is hydrogen, and n is an integer of 3. 7 General formula (fat 0: [In the formula, each X independently represents an argyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a purkylthio group having 1 to 5 carbon atoms, or a carbon atom selected from the group consisting of 1 to 6 alkylsulfinyl groups and N,N-di(alkyl)amino groups having 1 to 6 carbon atoms in each alkyl group, R1 being hydrogen, 2 to 6 carbon atoms; R2 is selected from the group consisting of alkanoyl groups of 1 to 3 carbon atoms and alkali metal ions, R2 is selected from the group consisting of alkyl groups of 1 to 3 carbon atoms, allyl groups and haloallyl groups, and R3 is selected from the group consisting of 8. The compound according to any one of claims 1 to 5, wherein X is selected from alkyl groups, and R' is hydrogen.8. selected from the group consisting of N,N-dimethylamino, R1 is selected from hydrogen, carbon atoms, 2 to 6 alkanoyl groups, sodium and potassium, and R2 is ethyl, n-propyl R3 is selected from the group consisting of ethyl group and n-propyl group, and n is 1-3
The compound according to any one of claims 1 to 7, which is selected from an integer of . 9,'2-(1-(ethoxyimino)propylcou 3-
Hydroxy-5-(5-(2,4,6-)rimethoxybilimidyl)]]Cyclohexy-2-en-1-one 2-
(1-(ethoxyimino)propyl-3-hydroxy-5-[5-(2,4,6-drimethylpyrimidyl)]
]Cyclohexy-2-en-1-one 2-[:1-(ethoxyimino)butyl]-3-hydroxy-5-(5-
(2-methylpyrimidyl)]]cyclohexy-2-en-1-one 2-(1-(ethoxyimino)gtyl)-3
-Hydroxy-5-[5-(2-methylthiopyrimidyl)]]cyclohexy-2-en-1-one and 2-[1'
l-(ethoxyimino)butyl]-3-hydroxy-5
-(:5-(2-nodoxypyrimidyl)]]cyclohexy-2-ene-1-oncara patent "
11. The compound according to any one of Items 1 to 5 or Item 8 of Item 11. 10 General formula (V): [In the formula, X and n represent those described in any one of claims 1 to 8, but when X is a methoxy group, , n does not represent 3]. 11. General formula (Va): [In the formula, X is any one of claims 1 to 8
[representing the compounds listed in Section]. [In the formula, X, R and n represent the compounds described in any one of claims 1 to 8]. 13. Compound of the general formula (XTI) [wherein X, R, R and n represent any one of claims 1 to 8] 14. General active ingredient Formula (■): [In the formula, X is the same or different; each independently represents a halogen; a nitro group; a cyano group; an alkyl group having 1 to 6 atoms; /% halogen; , a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms substituted with a substituent selected from the group consisting of an alkylthio group having 1 to 6 carbon atoms; Alkenyl group having 2 to 6 carbon atoms; Alkynyl group having 2 to 6 carbon atoms: 11-1-1oxy group; Alkoxy group having 1 to 6 carbon atoms; halogen and 1 to 6 carbon atoms Alkoxy group having 1 to 6 carbon atoms substituted with a substituent selected from the alkoxy groups of: alkenyloxy group having 2 to 6 carbon atoms; alkyloxy group having 2 to 6 carbon atoms: carbon Alkanoyloxy group having 2 to 6 atoms; alkoxycarbonyl group having 1 to 6 carbon atoms in the alkoxy group; alkylthio group having 1 to 6 carbon atoms: (7) argyl having 1 to 6 carbon atoms Sulfinyl group; alkylsulfonyl group having 1 to 6 carbon atoms; sulfamoyl group: N-alkylsulfamole group having 1 to 6 carbon atoms in the argyl group; name N,N-dialkylsulfamoyl group having a carbon atom: benzyloxy group; benzene ring is halogen, nitro group, alkyl group having 1 to 6 carbon atoms, 1 to 6 carbon atoms
I6 with 1 to 3 substituents selected from the group consisting of alkoxy groups and haloalkyl groups having 1 to 6 carbon atoms;
Substituted benzyloxy group: group NR5R' (in the formula, R5 and R6 are each independently hydrogen, a group having 1 to 1 carbon atoms)
6 argyl groups, C2-6 alkanoyl groups, benzoyl groups and benzyl groups); formyl groups and C2-6 alkanoyl groups, and their oximes and imines and Schiff's base derivatives, R' i, j: hydrogen; up to 1 carbon atoms, 6 alkyl groups; 2 to 6 carbon atoms;
6 alkenyl groups; alkynyl groups having 2 to 6 carbon atoms; alkoxy groups in which the alkyl group has 1 to 6 carbon atoms;
Alkylthio groups having 1 to 6 carbon atoms, phenyl groups and substituted phenyl groups (benzene ring is halogen, nitro group, cyano group, alkyl group having 1 to 6 carbon atoms, haloalthio group having 1 to 6 carbon atoms) I7 is substituted with 1 to 3 substituents selected from the group consisting of a C1-C6 alkoxy group, a C1-C6 alkylthio group,
1 with a substituent consisting of 11? Substituted alkyl group having 1 to 6 carbon atoms; Alkylsulfonyl group having 1 to 6 carbon atoms; Benzene sulfonyl group; Benzene ring halogen, Nido r7 group, cyano group, 1 to 6 carbon atoms 1 to 3 substituents selected from the group consisting of argyl groups having 1 to 6 carbon atoms, haloalkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and alkylthio groups having 1 to 6 carbon atoms. a substituted benzenesulfonyl group substituted with a nacyl group; and an inorganic or organic cation, R2 is an alkyl group having 1 to 6 carbon atoms;
-6 alkenyl group; haloalkenyl group having 2 to 6 carbon atoms; alkyl group having 2 to 6 carbon atoms = i4: Di haloarginyl group having 2 to 6 atoms; and alkyl group is halogen, carbon atom Alkoxy group with 1 to 6 carbon atoms, argylthio group with 1 to 6 carbon atoms, phenyl group, and benzene ring are halogen, nitro group, cyan group, carbon atoms'&i1
~1 of the substituents selected from the group consisting of 6 alkyl groups, haloalkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and argylthio groups having 1 to 6 carbon atoms 1 carbon atom substituted with a substituent selected from the group consisting of substituted phenyl groups substituted with ~3
~6 F-substituted alkyl groups, R is an alkyl group having 1 to 6 carbon atoms, 1 to 6 carbon atoms;
selected from the group consisting of 6 fluoroalkyl groups, alkenyl groups having 2 to 6 carbon atoms, alkynyl groups having 2 to 6 carbon atoms, and phenyl groups, and R is hydrogen, halogen, cyan group, or carbon atom number. selected from the group consisting of 1 to 6 alkyl groups and alkoxycarbonyl groups having 1 to 6 carbon atoms in the alkoxy group;
and n represents an integer of 1 to 3] and a supporting substance thereof. 15. An effective amount of the compound according to any one of claims 1 to 9 or the effective amount of M to an undesired plant or a growth medium for the plant.Claim 14. 16. A method for strongly damaging or killing undesired plants comprising applying the composition described in any one of claims 1 to 9 to a dicotyledonous crop or its growth medium. A compound as described or a composition as claimed in claim 14 in an amount sufficient to strongly damage or kill monocotyledonous weeds, but insufficient to substantially damage said crop. A method for selectively controlling the growth of monocot weeds in dicotyledonous crops.
The compound according to any one of Items 3 to 9 or q! "
The composition according to claim 14 is applied to Qi cotyledonous plants.
b. Growth of monocotyledonous weeds in cultivated crops consisting of applying a forceful (R) to the grass in an amount sufficient to damage or kill the grass, but insufficient to substantially damage said crop. A method for selectively controlling 18 compounds.
Apply at a rate in the range of 0 kg/l? ='r Claims IU
I8t'! : The method according to any one of Items 15 to 17. Δ1-I-2-1): t 19, General formula (I): [In the formula, an alkyl group having 1 carbon atom substituted with a substituent selected from the group consisting of halogen, nitro group, hydroxy group, alkoxy group having 1 to 6 carbon atoms, and alkylthio group having 1 to 6 carbon atoms; ~6 alkyl groups; 2 carbon atoms ~
6 alkenyl groups; alkynyl groups having 2 to 6 carbon atoms; to hydroxy: alkoxy groups having 1 to 6 carbon atoms; substituents selected from halogen and alkoxy groups having 1 to 6 carbon atoms; Substituted alkoxy group having 1 to 6 carbon atoms; Alkenyloxy group having 2 to 6 carbon atoms; °rrukynyloxy group having 2 to 6 carbon atoms; base alkanoyloxy group having 2 to 6 carbon atoms; ;Alkoxycarbonyl group having 1 to 6 carbon atoms in the alkoxy group;Alkylthio group having 1 to 6 carbon atoms:Number of carbon atoms 1
~6 alkylsulfinyl group: alkylsulfonyl group having 1 to 6 carbon atoms; sulf/T moyl group; N-alkylsulfamoyl group having 1 to 6 carbon atoms in the alkyl group; each alkyl group N,N-dialkylsulfamoyl group having 1 to 6 carbon atoms: penzyloxy group; benzene ring carhalogen, nitro group, number of carbon atoms 1
Substituted benzyloxy substituted with 1 to 3 substituents selected from the group consisting of ~6 alkyl groups, alkoxy groups having 1 to 6 carbon atoms, and haloalkyl groups having 1 to 6 carbon atoms group; a group NR5R' (wherein R5 and R6 are each independently selected from the group consisting of hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkanoyl group having 2 to 6 carbon atoms, a benzoyl group, and a benzyl group; R1 is hydrogen; an alkyl group of 1 to 6 carbon atoms; carbon Alkenyl group having 2 to 6 atoms: Alkynyl group having 2 to 6 carbon atoms: Alkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, alkylthio group having 1 to 6 carbon atoms, phenyl group, and substituted Phenyl group (Hensen ring halogen, nitro group, cyano group, alkyl group having 1 to 6 carbon atoms, haloalkyl group having 1 to 6 carbon atoms,
Alkoxy group having 1 to 6 carbon atoms and 1 to 6 carbon atoms
monochromatic, substituted alkyl groups having 1 to 6 carbon atoms substituted with a substituent consisting of 1 to 3 I substituents selected from the group consisting of 6 alkylthio groups;
Alkyl sulfonyl group having 1 to 6 carbon atoms; Benzene sulfonyl group: benzene ring is halokene, nitro group, cyan group, alkyl group having 1 to 6 carbon atoms, 1 carbon atom
Substituted benzenesulfonyl substituted with 1 to 3 substituents selected from fif consisting of ~6 haloalkyl groups, alkoxy groups having 1 to 6 carbon atoms, and alkylthio groups having 1 to 6 carbon atoms selected from the group consisting of a group; an acyl group; and an inorganic or organic cation; R2 is an argyl group having 1 to 6 carbon atoms;
~6 alkenyl group: haloalkenyl group having 2 to 6 carbon atoms; arginyl 215 having 2 to 6 carbon atoms:
k7 Haloal imaginary group having 2 to 6 atoms; and an alkyl group having a halogen, an alkoxy group having 1 to 6 carbon atoms, an alkylating agent having 1 to 6 carbon atoms; , a phenyl group, and a benzene ring Kahalogen, nitro group, cyano group, alkyl group having 1 to 6 carbon atoms, haloalkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, and alkylthio having 1 to 6 carbon atoms Substituted phenyl substituted with 1 to 3 substituents selected from the group consisting of 1 to 6 carbon atoms substituted with an f1° substituent selected from the group consisting of゛Selected from the group consisting of argyl groups, R3 is an alkenyl group having 1 to 6 atoms, a fluoroalkyl group having carbon atoms f, k 1 to 6117; l, an alkenyl group having 2 to 6 carbon atoms; i selected from the group consisting of alkynyl groups having 2 to 6 carbon atoms and phenyl groups
t. selected from the group consisting of 6 alkyl groups and alkoxycarbonyl groups having 1 to 6 carbon atoms in the alkoxy group, where n represents an integer of 1 to 3]. 2 of formula (Xlll) [in the formula, X1R3, R4 and n represent the above]
-acyl-5-(aryl)cyclohexane-J,3-
A dione derivative is reacted with an alkoxyamine derivative of the general formula (XVI): ■■2NOR2 [wherein R2 represents the above] to produce a compound of the formula (■): or a compound of the general formula (Xlll) 2
-Acyl-5-(aryl)cyclohexane-1.3-
A dione derivative is reacted with hydroxylamine to form an ogishim intermediate of the general formula (XVITI): [wherein X, R%R and n represent the above]. is a group to be eliminated] with an alkylating agent to produce a compound of general formula (II), and optionally, a compound of general formula (1) is converted into a compound of general formula (XX) :R'
1. A method for producing a cyclohexane-1,3-dione derivative, which comprises reacting with a compound of L [wherein is a group to be eliminated] to produce a compound of general formula (1). In order to synthesize a pyrimidine-5-carboxaldehyde derivative of the general formula (VB): [wherein X represents the compound described in claim 1], the general formula (XXI) [in the formula R has 1 to 6 carbon atoms
A pyrimidine produced by reacting a 2-methylenepropanediilidene conductor of 2-methylene propane diylidene selected from 2 alkyl groups with an amidine derivative or a salt thereof of the general formula - A method for producing a 5-carboxaldehyde derivative.