JP2002520384A - Aryl vinyl ether derivatives and their use as herbicides - Google Patents

Abstract

(57) Abstract: The present invention relates to aryl vinyl ether derivatives of the general formula (I) (wherein the substituents are defined in the description of the present specification), compositions containing them, methods for their preparation and intermediates The invention relates to a body and to a method for controlling weeds with such a composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]Background of the Invention  The present invention relates to novel aryl vinyl ethers having herbicidal activity and compositions containing them.
, Methods for producing them, intermediates thereof, and methods for controlling weeds with such compositions
Method and aryl vinyl ethers using detoxification or mitigation (poisonous mitigation) compounds
Related to the reduction of toxicity of tel (toxicity reduction).

[0002] One of the objects of the present invention is to provide novel aryl vinyl ether derivatives which are useful as very effective herbicides, and methods for their production.

[0003] Another object of the present invention is to provide herbicides that are effective against broadleaf and grass weeds.

[0004] Another object is to provide herbicides with selective herbicidal activity.

[0005] Another object is to provide herbicides that are effective with small amounts of herbicides.

[0006] Another object is to provide herbicides with good residual efficacy.

[0007] Many herbicides that may harm agricultural crops are known in terms of herbicide application rates (application rates) necessary for controlling (suppressing) the growth of weeds. This makes many herbicides unsuitable for weed control when certain crops are present. However, if weed growth cannot be controlled in crops, weeds and crops compete for nutrients, sunlight, and water, resulting in lower yields and lower crop quality. Reducing herbicide harm to crops without unacceptable loss of herbicidal action can be accomplished using crop protectants known as "antidote", which are known as "toxicants". Agent) "or" antagonist ".

[0008] The aryl vinyl ether compounds under certain conditions can be harmful to crops, especially to cereals such as corn and wheat, and thus a further object of the present invention is a method of reducing harm to crops by aryl vinyl ether compounds. It is to provide.

[0009] These and other objects of the present invention can be achieved in whole or in part by the compounds of the present invention.

[0010]Description of the invention  The present invention provides compounds of formula (I):

[0011]

Embedded imageWherein p is 0 or 1, X¹Is O, NH, or S; X²Is O, S, NR¹⁸Or a single bond (preferably O, S, NR¹⁸)so
Yes; X³Is N or CR¹⁹R¹⁷And R¹⁸Are independently a hydrogen atom or an optionally substituted group R²⁰,
R²¹, R²²Or R²³Where: R²⁰Represents a lower alkyl group; R²¹Represents a lower alkenyl group; R²²Represents a lower alkynyl group; R²³Is-(CH₂)_m-Represents a phenyl group; m represents 0 or 1;¹⁶Is R²⁴, OR²⁵, SR²⁵, NR²⁵R²⁶Or
Alkyl substituted with alkoxycarbonyl; R²⁴, R²⁵, And R²⁶Is independently R¹⁸Has one of the meanings given to
R;¹⁹Is R¹⁶R has one of the meanings given above; R¹⁰Is -CH₂NO₂, -CHR²⁷R²⁸, -CR²⁷R²⁸R²⁸¹, -CR^{3 0} R²⁹R²⁹¹, -CO-NR³⁰R³¹, -CH₂NR³⁰R³¹, -CH
= CR³¹R³², -CH₂N (R³⁰) S (O)_qR³³, -C (O) SR^{3 2} , -CH₂C (O) SR³²,-(CH₂)_zCO₂R³², -CO₂R³² , -CH = CHC (O) OR³², -C (R³²) = N-NR³⁰R³¹, -C
(R³²) = N—NH—C (O) lower alkyl, —COR³², -C (O) OC
(O) R³², -C (= N-OH) R³², -C @ CCOOR³², -CH₂S
CN, -CH₂NCO, -CH₂NCS, -CH₂N₃, -CH₂CN, -CH ₂ OSCN, -CH₂OCN, -CH₂N (R³⁰) CO₂R³³, -CH₂O
SO₂R³³, -CH₂SO₂OR³³, -CH₂OCO₂R³³, -CH = C
HNR³³R³⁴, -C (O) ONR³³R³⁴, -C (= NR³⁵) R³²,
-CH₂P (O) R³⁵R³⁶, -CH₂OP (O) R³⁵R³⁶, -CH₂O
C (O) NR³⁰R³⁶, -CH₂OCH₂C (O) (optionally substituted phenyl
), -CO₂N = C (optionally substituted phenyl)₂, N-succinimide
Tyl, N-phthalimidomethyl, tetrazolyl group (particularly 1-tetrazolyl),-
CONNHHR³⁰, -CO₂CH₂CO (optionally substituted phenyl or
Is saturated or unsaturated containing 1 to 3 heteroatoms selected from O, N, and S
5-7 membered heterocycle of the sum), -CO₂CH₂(1 to 1 selected from O, N, and S
Saturated or unsaturated 5-7 membered heterocycle containing 3 heteroatoms), CO₂R^32a , COCH₂COR³³, COCHN₂, CONH (lower hydroxyl group substituted with hydroxyl group)
Alkyl), -CH (OH) (lower alkyl), C (R³²) = N-NH-C (S
) NR^a, C (R³²) = N-NH (optionally substituted, selected from O, N, and S)
Selected unsaturated 5-7 membered heterocycle containing 1-3 heteroatoms), C (R³²)
= N-NR^30aR^31a, C (R³²) = N-NHSO₂R³³, And C (
O) represents a group selected from: F, z represents 1, 2, 3, or 4; q represents 0 or 2; R^aRepresents H or lower alkyl; R^32aIs an N-linked imidazo optionally substituted and optionally fused to a benzene ring
A ring or a triazole ring; R^30aAnd R^31aAnd the N atom to which they are attached
O, S or NR^aA 5- or 6-membered saturated heterocycle optionally containing a group in the ring
Forming; R²⁷, R²⁸, And R²⁸¹Represents a same or different halogen atom; R²⁹And R²⁹¹Is OR³⁷Or SR³⁷Or R²⁹And R²⁹¹Form a divalent group and combine with
Combined carbon atoms are 5- or 6-membered cyclic acetal or thioacetal ring
Wherein the ring structure is optionally substituted with one or more lower alkyl groups;³⁰, R³¹, And R³²Is independently hydrogen, lower alkyl, lower haloal
Kill, lower alkoxyalkyl, lower alkenyl, lower haloalkenyl, lower
Ruquinyl, lower haloalkynyl, optionally substituted cycloalkyl, optionally substituted
-(CH₂)_mRepresents phenyl; R³³And R³⁴Is R other than a hydrogen atom³²R;³⁵And R³⁶Represents a hydrogen atom or represents an alkyl, alkoxy, or
Or a group which may be any of optionally substituted phenyl; R³⁷Is lower alkyl, lower haloalkyl, lower alkenyl, or lower ha.
R represents alkenyl; R¹¹And R¹³Each independently represents hydrogen or alkyl, or
Is R¹¹And R¹³Together form a single bond, together with the carbon atom to which they are attached
May form a double bond, or R¹¹And R¹³Is a divalent group containing 1 to 6 atoms in the main chain.
The main chain can be one to three nitrogen atoms, one oxygen atom, or one sulfur atom.
Optionally containing an atom; the sum of the divalent group and the two carbon atoms to which it is attached
Is a saturated or unsaturated carbocyclic or heterocyclic ring (eg, phenyl or pyridyl)
) Or a bicyclic ring, wherein these rings have 1 to 4 R^FifteenOptionally by group
Substituted, each ring is up to 8 members, preferably up to 6 members, R^FifteenRepresents a halogen atom, a hydroxyl group, cyano, lower alkoxycarbonyl, lower
Alkyl, lower alkenyl, lower alkynyl, optionally substituted cycloalkyl
, Lower alkoxy, lower alkylthio, lower alkylsulfinyl, lower alkyl
Rusulfonyl, lower haloalkoxycarbonyl, lower haloalkyl, lower haloa
Lucenyl, lower haloalkynyl, halocycloalkyl, lower haloalkoxy, lower
Lower haloalkylthio, lower haloalkylsulfinyl, lower haloalkylsulfo
Nil, nitro, amino, lower alkylamino, lower dialkylamino, optional
Substituted phenoxy, lower alkylcarbonylamino, carbamoyl, lower alkyl
Kilcarbamoyl, lower dialkylcarbamoyl, -CH₂SCN, SF₅, −
CR³⁰= N-R³¹, -CR³⁰= NOR³¹, -CR³⁰= NNR³⁰R^{3 1} , -CR³⁰R²⁹R²⁹¹, Alkoxyalkyl, CR^bR^cR^a, COR ^a Is optionally substituted phenyl or naphthyl, or alkoxy
Carbonyl or CO₂R represents alkenyloxy substituted with H;^bAnd R^cAnd the C atom to which these are bonded are a 5- or 6-membered ring
Forming an acetal group; or R¹⁰R¹¹R¹²CC (R¹³) (R¹⁴)-Is a group (A), (B
), (C), (D), or (E):

[0012]

Embedded imageWherein R is^d, R^e, R^f, R^g, And R^hIs H, lower alkyl, halo
And n represents a value of 0, 1, 2, or 3; R¹⁵¹Is R^FifteenOr a hydrogen atom; R¹²And R¹⁴Each independently represents hydrogen or alkyl, or
May form a double bond together with a single bond, in which case R¹¹And R¹³ Are combined to form one divalent group; preferably, the following condition is satisfied; i) R¹⁰R¹¹R¹²CC (R¹³) (R¹⁴)-Is R^FifteenArbitrarily
Represents a substituted phenyl ring;¹⁰Is -CO₂R³², CONR³⁰R³¹, C
HR²⁷R²⁸Or CR²⁷R²⁸R²⁸¹And R in the formula³²Is archi
R or haloalkyl; R³⁰And R³¹Represents H or alkyl;
R²⁷, R²⁸, And R²⁸¹Is as defined above; p is 0; X ₁ Is O; X₂Is O; X₃Is CH; R¹⁶Is OR²⁵Place that is
If; R^FifteenIs not a monohalomethyl group; ii) R¹⁰R¹¹R¹²CC (R¹³) (R¹⁴)-Is EtO₂C-CH
= CH-; p is 1; X₁Is S; X₂Is a bond; R¹⁷ Represents phenyl; X₃Is CH; R¹⁶Is NH₂And NMe₂not
Iii) R¹¹, R¹², R¹³, R¹⁴Each represents H; p is 1
R; X₁Is S and X₂Is O; R¹⁷Represents Et; X₃Is N;
R¹⁶Represents -NH (4-nitrophenyl); R¹⁰Is CO₂H and CON
Not HPh; iv) R¹¹, R¹², R¹³, R¹⁴Each represents H; p is 0 and
X₁Is S and X₂Is O; R¹⁷Represents Et; X₃Is N; R ¹⁶ Represents -NH (4-nitrophenyl); R¹⁰Is CO₂H and CONH ₂ Not; v) p represents 0; X₁Is O; X₂Is a bond; R¹⁷Represents H;
X₃Is CH; R¹⁶Is NMe₂R;¹⁰R¹¹R¹²CC (R^{1 3} ) (R¹⁴)-Is 5-methyl-2-R¹⁰Represents a -substituted-thien-3-yl group
Case; R¹⁰Is CO₂H and CO₂Not Me; vi) R¹¹, R¹², R¹³, R¹⁴Each represents H; p is 0 and
X₁Is S and X₂Is O; R¹⁷Represents H; X₃Is N; R^{1 6} Is -NH (4-nitrophenyl); R¹⁰Is CO₂Not H; vii) R¹⁰Is CO₂Represents Et; R¹¹, R¹², R¹³, And R¹⁴ Each represents H; p is 0;₁Is S; X₂Is NH and R^{1 7} Represents phenyl; X₃Is CMe; R¹⁶Is NH₂And in NHMe
None; viii) p is 0; X₁Is O; X₂Is O; R¹⁷Is Me
Represents; X₃Is CH; R¹⁶Represents OMe; R¹⁰R¹¹R¹²CC (
R¹³) (R¹⁴)-Is 1,3-dimethyl-4-R¹⁰-Substituted-pyrazole-5
-Yl group; R¹⁰Is not 4-chlorobenzoyl] and their agriculturally acceptable salts and metal complexes, which are useful
Has herbicidal properties.

The compounds of formula (I) mentioned in the above conditions i) to viii) are not considered to themselves form part of the present invention, but their use as herbicides and compositions containing them Should be understood as forming part of the present invention.

The present invention further encompasses any stereoisomer, optical isomer, geometric isomer of formula (I), or a mixture thereof.

The aryl vinyl ether derivatives of the present invention have two possible stereoisomers (Z) and (E) isomers at the position of the double bond, defined according to the Cahn-Ingold-Prelog rules. Has a body. The present invention is to be understood as embracing both the pure isomers or the mixtures, either of which may be enriched. Further, R ¹⁰ , R ¹¹ , R ¹² , R ¹³ ,
R ^14, and ^{R 17} are as defined in above, _{X 3} is ^{CR 19, R 1 6} is ^{OR 25,} compounds of formula (I) where ^{R 25} is hydrogen, their It will also be appreciated that tautomeric and acetal forms may exist.

The term “agriculturally acceptable salts” means salts whose cations or anions are known and accepted in the art of salt formation for agricultural or horticultural uses. Suitable salts with a base include alkali metals (eg, sodium and potassium), alkaline earth metals (eg, calcium and magnesium), ammonium, and amines (eg, diethanolamine, triethanolamine, octylamine, morpholine, and Dioctylmethylamine). Suitable acid addition salts formed, for example, from compounds of formula I that contain an amino group include salts with inorganic acids, for example, salts with organic acids such as hydrochloride, sulfate, phosphate, and nitrate, and acetic acid. Is mentioned.

The formyl group can be present in the form of a hydrate, ie in the form of dihydroxymethyl.

In the above definitions used in formula (I), all of the optionally substituted groups can have one or more halogen atoms, especially as optional substituents, among the possible substituents.

As the optional substituent of the cycloalkyl group, lower alkyl, lower alkenyl, lower alkynyl, lower haloalkyl, and halogen can be particularly selected.

Examples of the optional substituent of the phenyl group include phenoxy, lower alkyl, lower alkenyl, lower alkynyl, lower haloalkyl, cyano, lower alkoxycarbonyl, lower haloalkoxycarbonyl, lower alkoxy, lower haloalkoxy,
Lower alkylthio, lower haloalkylthio, lower alkylsulfonyl, lower haloalkylsulfonyl, lower alkylsulfinyl, lower haloalkylsulfinyl, nitro, lower alkylcarbonyl, lower alkylamino, lower dialkylamino, carbamoyl, lower alkylcarbamoyl, lower dialkylcarbamoyl, lower alkylcarbonyl Amino and phenyl optionally substituted with halogen, alkyl, alkoxy, or benzyloxy can be selected.

In this patent specification, including the appended claims, certain atoms and groups have the following meanings: a halogen atom means fluorine, chlorine, bromine, or iodine; an alkyl group, Alkenyl groups and alkynyl groups may be straight-chain or branched-chain; cycloalkyl has 3 to 6 carbon atoms in the ring; lower in the group is straight-chain or branched. It means that the group can contain up to 8 carbon atoms, preferably up to 6 carbon atoms.

Among the compounds represented by the above general formula (I), a preferred compound group is
In general formula (I), R¹¹And R¹³Is replaced by a halogen atom (preferably chlorine or fluorine)
Forming an unsaturated carbocycle (preferably phenyl);¹¹And R¹³But
Represents a pyridine ring; or R¹¹And R¹³Represents a phenyl ring, and this is the o-position
And m-position (R¹⁰With a saturated or unsaturated 5- or 6-membered carbocyclic ring
Combination; X₃Is CR¹⁹And R¹⁹Represents a hydrogen atom; X₂Is an oxygen atom; X₁Is an oxygen atom or a sulfur atom (preferably an oxygen atom);¹⁶Is a hydrogen atom or a lower alkyl group (preferably methyl), or OR ²⁵ (R²⁵Represents a lower alkyl group or a hydrogen atom) (most preferably
R¹⁶Is methoxy); R¹⁷Is a hydrogen atom or a lower alkyl group (preferably methyl)
No.

R¹⁰Is -CHR²⁷R²⁸(Where R²⁷And R²⁸Is preferably bromine
Or -COR³²Or -CO₂R³²(Where R³²Is preferred
Or lower alkyl or hydrogen), or -CH₂OSO₂R³³(Preferred
Kuha R³³Represents substituted phenyl), or -CH₂NO₂Or -CH₂O
CH₂C (O) Ph or -CH₂OTs, or -C (R³²) = N-NH
SO₂R³³(Where R³²Is hydrogen and R³³Is lower alkyl),
Or -C (R³²) = N-NH-C (S) NR^a(Where R³²Is hydrogen,
R^aIs lower alkyl), or -C (R³²) = N-NR³⁰R³¹(This
Where R³²And R³⁰Is hydrogen and R³¹Is optionally substituted-(CH₂) _m -Phenyl) or -C (R³²) = N−N^30aR^31a(here
R³²Is hydrogen and R^30aAnd R^31aTogether with the N atom to which they are attached
And further O and NR^aA 6-membered saturated heterocyclic ring containing a group in the ring),
Or -C (R³²) = N-NH (optionally substituted nitrogen-containing unsaturated 6-membered compound)
Ring) (where R³²Is hydrogen), or -C (O) F, or -CO₂C
H₂CO (optionally substituted phenyl), or -CO₂R^32a(Where R^{3 2a} Is an optionally substituted N-linked triazole ring fused to a benzene ring)
Or -CO-NR³⁰R³¹(Where R³⁰Is hydrogen and R³¹Is a lower class
Alkyl)), or -CONNHHR³⁰(Where R³⁰Is optionally replaced
-(CH₂)_m-Phenyl) or -C (R³²) = NNH-C (O
) Lower alkyl (where R³²Is hydrogen), or -C (O) SR³²(This
Where R³²Is lower alkyl), or -CH (OH) lower alkyl;
Is -COCHN₂Or -CR³⁰R²⁹R²⁹¹(Where R³⁰Is hydrogen
R²⁹And R²⁹¹Are combined to form a divalent group, and this divalent group
An optionally substituted thioacetator of a 5-membered ring whose combined carbon atoms are
-C (= N-OH) R³²(Where R³²Is lower al
Kill)) or-(CH₂)_zCO₂R³²(Where R³²Is hydrogen, lower
Alkyl, lower alkenyl, lower alkynyl, lower haloalkyl, lower alkoxy
Cycloalkyl, optionally substituted-(CH₂)_m-Phenyl); or R¹⁰R¹¹R¹²CC (R¹³) (R¹⁴)-Is a group A (here
In R^dAnd R^eRepresents hydrogen or halogen); R^FifteenIs -COR^a, Or halogen, or lower alkyl, or lower
Alkoxy, or lower haloalkoxy, or lower alkoxycarbonyl, or
Is CR^bR^cR^a(Where R^bAnd R^cForms a 5-membered cyclic acetal group,^aIs
(Representing hydrogen) are also preferred.

A preferred class of compounds of formula (I) is: R¹¹And R¹³Is at least one halogen, alkyl or haloalkyl group
Forming a substituted phenyl or naphthyl ring; X₃Is CR¹⁹(R in the formula^{1 9} Represents a hydrogen atom); X₁And X₂Each represents an oxygen atom; ¹⁶ And R¹⁷Each represents a methyl group;¹⁰Is -CO₂R³²Is
Compound.

The most preferred class of compounds of formula (I) is:¹¹And R¹³Is at least one halogen, alkyl or haloalkyl group
Forming a substituted phenyl or naphthyl ring; X₃Is CR¹⁹(R in the formula^{1 9} Represents a hydrogen atom); X₁And X₂Each represents an oxygen atom; ¹⁶ And R¹⁷Each represents a methyl group;¹⁰Is -CO₂R³²Is
, This R³²Is a lower alkyl or hydrogen.

The following compounds are particularly preferred: 1.2- (2-t-butyloxycarbonyl-4-chlorophenoxy) -3-
Methyl methoxypropenoate; 2.2 Methyl 2- (2-carboxy-4-chlorophenoxy) -3-methoxypropenoate; 3.2 Methyl 2- (2-carboxy-4-iodophenoxy) -3-methoxypropenoate; Methyl 2- (2-dibromomethyl-4-chlorophenoxy) -3-methoxypropenoate; methyl methyl 2- (2-formyl-4-chlorophenoxy) -3-methoxypropenoate; 6.2- [4 -Chloro-2-((N-methyl-N-phenylamino) methyl)
Methyl phenoxy] -3-methoxypropenoate; 7.2- [4-Chloro-2- (N-allylamino) methyl) phenoxy] -3
-Methyl methoxypropenoate; 8.2- [4-Chloro-2- (N-benzylamino) methyl) phenoxy]-
9. 2- [4-chloro-2- (N-cyclopropylamino) methyl) phenoxy] -3-methoxypropenoic acid methyl; 10.2- [4-chloro-2- (azidomethyl) ) Methyl phenoxy] -3-methoxypropenoate; 11.2- [4-Chloro-2- (N-succinimidomethyl) phenoxy]-
12. 2- [4-chloro-2- (N-phthalimidomethyl) phenoxy] -3
13.2- [4-Chloro-2- (N-isopropyl-N- (methanesulfonyl) aminomethyl) phenoxy] -3-methylpropenoate; 14.2- [4-chloro-methyl-methoxypropenoate; Methyl 2- (N-methyl-N- (methanesulfonyl) aminomethyl) phenoxy] -3-methoxypropenoate; 15.2- [4-chloro-2- (N- (methoxycarbonyl) aminomethyl)
-Methyl phenoxy] -3-methoxypropenoate; 16.2- (4-Chloro-2- (nitromethyl) phenoxy) -3-methylpropenoate; 17.2- (4-Chloro-2- (cyanomethyl) phenoxy 18.2) -Methyl 3-methoxypropenoate; 18.2- (4-Chloro-2- (thiocyanomethyl) phenoxy) -3-methylpropanoate; 19.2- (4-Chloro-2-methoxycarbonylphenoxy) Methyl 2-methoxypropenoate; 20.2- (4-chloro-2-ethoxycarbonylphenoxy) -3-methoxypropenoic acid; 21.2- (4-chloro-2-N- (4-trifluoromethoxy) Phenyl)-
Methyl aminocarbonyl) phenoxy-3-methoxypropenoate; 22.2- (4-chloro-2-N- (2-chloro-4- (ethoxycarbonyl) phenyl) -aminocarbonyl) phenoxy-3-methoxypropenoate 23.2- (4-chloro-2-N- (3,5-difluorophenyl) aminocarbonyl) phenoxy-3-methoxypropenoate; 24.2- (4-chloro-2-N- (3- Trifluoromethylphenyl) aminocarbonyl) -phenoxy-3-methoxypropenoate; 25.2- (4-chloro-2-N- (3,5-dichlorophenyl) aminocarbonyl) phenoxy-3-methoxypropenoate; 26. 2- (4-chloro-2-N- (2,6-difluorophenyl) aminocarbonyl) phenoxy-3- 27.2- (4-chloro-2-N- (4-bromo-3-trifluoromethylphenyl) -aminocarbonyl) phenoxy-3-methoxypropenoate; 28.2- (4- Chloro-2-N- (3-chlorophenyl) aminocarbonyl) phenoxy-3-methoxypropenoate; 29.2- (4-chloro-2-N- (5-chloro-2-methylphenyl) aminocarbonyl) phenoxy 30.2- (4-chloro-2-N- (2,5-difluorophenyl) aminocarbonyl) phenoxy-3-methoxypropenoate; 31.2- (4-chloro- 2-N- (3-phenoxyphenyl) aminocarbonyl) phenoxy-3-methoxypropenoate; 32.2- (4-chloro-2-N -(3-bromo-5-trifluoromethylphenyl) aminocarbonyl) phenoxy-3-methoxypropenoate; 33.2- (4-chloro-2-N- (3,5-dibromophenyl) aminocarbonyl) phenoxy 34.2- (4-chloro-2-N- (5-methoxy-2-methylphenyl) aminocarbonyl) phenoxy-3-methoxypropenoate; 35.2- (4- Chloro-2-acetylaminoiminomethylenephenoxy)-
Methyl 3-propenoate; 36.2- (4-chloro-2-hydroxyiminomethylenephenoxy) -3-
Methyl propenoate; 37.2- (4-chloro-2-methoxyiminomethylenephenoxy) -3-methyl propenoate; 38.2- (4-chloro-2-ethoxyiminomethylene phenoxy) -3-methyl methyl propenoate; 39.2- (4-Chloro-2-allyloxyimino methylenephenoxy) -3
-Methyl propenoate; 40.2- (4-chloro-2-t-butyloxyimino methylene phenoxy)
41- (4-chloro-2-benzyloxyiminomethylenephenoxy)-
4methyl 2-propenoate; 42.2- (4-chloro-2-phenoxyiminomethylenephenoxy) -3-
Methyl propenoate; 43.2- (2-Carboxy-4-chlorophenoxy) -3-methoxypropenoic acid methyl, sodium salt; 44.2- (4-Chloro-2- (2-methoxycarbonylethenyl) phenoxy) Methyl 4-methoxypropenoate; 45.2- (2-carboxy-4-methylphenoxy) -3-methylpropenoic acid; 46.2- [2-carboxy-3- (2-methoxy-1-methoxycarbonyl) Methyl vinyloxy) phenoxy] -3-methoxypropenoate; 2,4-dichlorophenyl 47.2- (2-carboxy-4-chlorophenoxy)-(3-methoxy) thiopropenoate; 48.2- (2-carboxy- Methyl 4-chlorophenoxy) -3- (1-ethoxycarbonyl) ethoxypropenoate; 49.2- (2- Methyl carboxy-4-chlorophenoxy) -3-prop-2-ynyloxypropenoate; 50.2- {4-chloro-2- [N '-(2-chlorophenyl) hydrazinocarbonyl] phenoxy} -3- Methyl methoxypropenoate; 51.2- [4-Chloro-2- (prop-2-ynyloxycarbonyl) phenoxy] -3-methoxypropenoate; 52.2- [2- (benzyloxycarbonyl) -4 -Chlorophenoxy]-
Methyl 3-methoxypropenoate; 53.2- [4-chloro-2- (propyloxycarbonyl) phenoxy]-
Methyl 3-methoxypropenoate; 54.2- [2- (butyloxycarbonyl) -4-chlorophenoxy] -3
Methyl 5-methoxypropenoate; 55.2- [4-chloro-2- (prop-2-yloxycarbonyl) phenoxy] -3-methoxypropenoate; 56.2- [4-chloro-2- (3- Methyl chloropropyloxycarbonyl) phenoxy] -3-methoxypropenoate; 57.2-methyl 4-chloro-4- (but-2-yloxycarbonyl) phenoxy] -3-methoxypropenoate; 58.2- [ Methyl 4-chloro-2- (3-pentyloxycarbonyl) phenoxy] -3-methoxypropenoate; 59.2- [4-Chloro-2- (hept-2-yloxycarbonyl) phenoxy] -3-methoxypropene Acid methyl; 60.2- [4-chloro-2- (octyloxycarbonyl) phenoxy]-
61.2- [4-chloro-2- (cyclopentyloxycarbonyl) phenoxy] -3-methoxypropenoic acid methyl; 62.2- [4-chloro-2- (2-methoxyethoxycarbonyl) ) Methyl phenoxy] -3-methoxypropenoate; 63.2- [4-Chloro-2- (2-ethoxyethoxycarbonyl) phenoxy] -3-methoxypropenoic acid methyl; 64.2- [4-chloro-2- Methyl (cyclopropylmethoxycarbonyl) phenoxy] -3-methoxypropenoate; methyl 65.2- (4-methoxy-2-methoxycarbonylphenoxy) -3-methoxypropenoate; 66.2- [2- (benztriazole- 1-yloxycarbonyl) -4-
67.2- [4-chloro-2- (4-nitrophenoxycarbonyl) phenoxy] -3-methoxypropenoic acid methyl; 68.2- [4-chloro-2-methylchlorophenoxy] -3-methoxypropenoate; Methyl (2,4,5-trichlorophenoxycarbonyl) phenoxy] -3-methoxypropenoate; 69.2- [4-chloro-2- (2,3,4,5,6-pentachlorophenoxycarbonyl) phenoxy] 70.2- [4-Chloro-2- (ethylcarbamoyl) phenoxy] -methyl 3-methoxypropenoate; 71.2- [4-Chloro-2- (ethylthiocarbamoyl) phenoxy ] -3
-Methyl methoxypropenoate; 72.2 methyl 2- (2-carboxy-4-methoxyphenoxy) -3-methoxypropenoate; 73.2 butyl methyl 2- (2-carboxy-4-chlorophenoxy) -3-methoxypropenoate; 74.2 Methyl 2- (2-carboxy-3-fluorophenoxy) -3-methoxypropenoate; 75.2 Methyl methyl 2- (2-carboxy-3-chlorophenoxy) -3-methoxypropenoate; 76.2- (2 -Methyl carboxy-3-methylphenoxy) -3-methoxypropenoate; 77.2-methyl 2- (2-carboxy-4-chlorophenoxy) -3-methylthiopropenoate; 78.2- (2-carboxyphenoxy) -3 -Methyl methoxypropenoate; 79.2- (1-carboxynaphth-2-yloxy) -3-methoxy Methyl Ropen acid; 80.2- (2-carboxy-3,4-difluorophenoxy) -3-methoxy-propenoic acid methyl; 81.2- (2-carboxy-3-chloro-4-fluorophenoxy) -3-
Methyl methoxypropenoate; 82.2- (2-carboxy-4-chloro-3-fluorophenoxy) -3-
Methyl methoxypropenoate; 83.2-Methyl 2- (2-carboxy-4-difluoromethylphenoxy-3-methoxypropenoate; 84.2 Methyl methyl 2- (4-bromo-2-carboxyphenoxy) -3-methoxypropenoate; 85 Methyl 2- (2-carboxy-4-fluorophenoxy) -3-methoxypropenoate; methyl 86.2- (3-bromo-2-carboxyphenoxy) -3-methoxypropenoate; Methyl carboxy-3-thiocyanatomethylphenoxy) -3-methoxypropenoate; methyl 88.2- (3-acetoxymethyl-2-carboxyphenoxy) -3-methoxypropenoate; 89.2- (2-carboxy- Methyl 3,4-dichlorophenoxy) -3-methoxypropionate; 90.2- (2-carbo) 91.2- (3-Hydroxyphthalid-7-yloxy) -3-methoxypropenoic acid methyl; 92.2- {4-chloro-2-methyl methyl 3--3-dihydroxymethylphenoxy) -3-methoxypropenoate; [N ′-(2,4-dichlorophenyl) hydrazinocarbonyl] methyl phenoxy} -3-methoxypropenoate; 93.2- {4-chloro-2- [N ′-(3-trifluoromethylphenyl)
Methyl hydrazinocarbonyl] phenoxy} -3-methoxypropenoate; methyl 94.2- [2- (2,2,2-trifluoroethoxycarbonyl) phenoxy] -3-methoxypropenoate; 95.2- [4- Methyl chloro-2- (2,2,2-trichloroethoxycarbonyl) phenoxy] -3-methoxypropenoate; 96.2- {4-chloro-2-[(1-hydroxy-2-methylprop-2-);
98.2] [Methyl] carbamoyl] methyl phenoxy} -3-methoxypropenoate; 98.2 Methyl 2- [4-methyl-2- (2,2,2-trifluoroethoxycarbonyl) phenoxy] -3-methoxypropenoate; -(3-Fluoro-2-hexylthiocarbonylphenoxy) -3-
Methyl methoxypropenoate; 99.2- [4-Fluoro-2- (2-ethoxyethoxycarbonyl) phenoxy] -3-methyl methoxypropenoate; 100.2- (4-Bromo-2-methoxycarbonylphenoxy) -3 -Methyl-methoxypropenoate; 101.2-Methyl- (4-fluoro-2-methoxycarbonylphenoxy) -3-methoxypropenoate; 102.2- (2-Ethoxycarbonyl-3-fluorophenoxy) -3-methoxypropenoic acid Methyl; 103.2- [3-fluoro-2- (prop-2-ynyloxycarbonyl)
Methyl phenoxy] -3-methoxypropenoate; 104.2- (2-benzyloxycarbonyl-3-fluorophenoxy)-
Methyl 3-methoxypropenoate; 105.2- [3-Fluoro-2- (2-methoxyethoxycarbonyl) phenoxy] -3-methylpropoxylate; 106.2- [2- (2-ethoxyethoxycarbonyl)- Methyl 3-fluorophenoxy] -3-methoxypropenoate; 107.2-Methyl 3-fluoro-2- (tetrahydrofuran-2-ylmethoxycarbonyl) phenoxy] -3-methoxypropenoate; 108.2- [2- Methyl (3-chloropropyloxycarbonyl) -3-fluorophenoxy] -3-methoxypropenoate; 109.2-Methyl 2- (2-butyloxycarbonylphenoxy) -3-methoxypropenoate; 110.2- (2-pentyl) Methyl oxycarbonylphenoxy) -3-methoxypropenoate; 1 11.2-Methyl 2- (2-octyloxycarbonylphenoxy) -3-methoxypropenoate; 112.2- [2- (3-chloropropyloxycarbonyl) phenoxy]-
Methyl 3-methoxypropenoate; 113.2- [2- (prop-2-ynyloxycarbonyl) phenoxy]-
Methyl 3-methoxypropenoate; Methyl 114.2- (2-benzyloxycarbonylphenoxy) -3-methoxypropenoate; Methyl 115.2- (2-carboxy-3,4-difluorophenoxy) -3-methoxypropenoate 116.2- (2-Carboxy-4-iodophenoxy) -3-methylpropenoic acid methyl, sodium salt; 117.2- [3-Methyl-2- (4-methylbenzyloxycarbonyl) phenoxy] -3- Methyl methoxypropenoate; 118.2- [2- (2-ethoxyethoxycarbonyl) -3,4-difluorophenoxy] -3-methoxypropenoic acid methyl; 119.2- [3,4-difluoro-2- (4 -Methylbenzyloxycarbonyl) phenoxy] -3-methoxypropenoic acid methyl; 122-Methyl 2- (2-benzyloxycarbonyl-3,4-difluorophenoxy) -3-methoxypropenoate; 122.2-Methyl 2- [4- (4-methylbenzoylmethoxycarbonyl) phenoxy] -3-methoxypropenoate; 122 Methyl 2- [4-fluoro-2- (4-methylbenzoylmethoxycarbonyl) phenoxy] -3-methoxypropenoate; 123.2- [2- (4-nitrobenzoylmethoxycarbonyl) phenoxy] -3-methoxypropene Methyl 124.2- [2- (3,4-dichlorobenzoylmethoxycarbonyl) phenoxy] -3-methoxypropenoate; 125.2- [2- (4-cyanobenzoylmethoxycarbonyl) phenoxy] -3- Methyl methoxypropenoate; 126.2- [4-chloro Methyl 2- (benzoylmethoxycarbonyl) phenoxy] -3-methoxypropenoate; 127.2-Methyl 2- (benzoylmethoxycarbonyl) phenoxy] -3-methoxypropenoate; 128.2- [4-chloro-2- Methyl (diphenylmethyleneiminooxycarbonyl) phenoxy] -3-methoxypropenoate; 129.2- [4-chloro-2- (3-cyclopropyl-3-oxopropanoyl) phenoxy] -3-methoxypropenoate; 130.2- [2- (pyrid-2-ylhydrazonomethylene) phenoxy]-
131.2- [4-Chloro-2- (N-methylsulfonylhydrazonomethylene) phenoxy] methyl 3-methoxypropenoate; 132.2- [4-Chloro-2- (2 Methyl 3,4,6-trichlorophenylhydrazonomethylene) phenoxy] -3-methoxypropenoate; 133.2- {4-chloro-2- [N- (4-morpholinyl) iminomethylene] phenoxy} -3-methoxypropene Methyl 134.2- [4-chloro-2- (pyrid-2-ylhydrazonomethylene) phenoxy] -3-methoxypropenoate; 135.2- [4-chloro-2- (4-fluorophenyl) Methyl hydrazonomethylene) phenoxy] -3-methoxypropenoate; 136.2- [4-chloro-2- (4-nitrophene) Le hydrazono methylene)
137.2- {4-Chloro-2- [N- (dimethylthiocarbamoyl) hydrazonomethylene] phenoxy) -3-methoxypropenoic acid methyl; 138.2- [4-Methoxypropenoic acid methyl; Methyl chloro-2- (1,3-dithiolan-2-yl) phenoxy] -3-methoxypropenoate; 139.2- [2-methoxycarbonyl-3- (2-methyl-1,3-dioxolan-2-) Yl) phenoxy] -3-methoxypropenoic acid methyl; 140.2- (2-methoxycarbonylbenzyloxy) -3-methoxypropenoic acid methyl; 141.2 .- (3-acetyl-2-methoxycarbonylphenoxy) -3- Methyl methoxypropenoate; 142.2- [4-chloro-2- (1-hydroxyethyl) phenoxy] -3
143.2- [4-Chloro-2- (diazoacetyl) phenoxy] -3-methylpropenoate; 144.2- [4- (3-acetamidophenyl) -2-carboxyphenoxy] 145.2- {2-Carboxy-4- [3-fluoro-4-phenyl] phenylphenoxy} -3-methoxypropenoic acid methyl; 146.2- [2-carboxy-4-methyl (Naphth-2-yl) phenoxy] -3
147.2- [4- (4-benzyloxyphenyl) -2-carboxyphenoxy] -3-methylmethyl methoxypropenoate; 148.2- [2-carboxy-4- (benzo-1, 3-dioxolan-5-
Il) Methyl phenoxy] -3-methoxypropenoate; 149.2- [4-Chloro-2- (methoxymethoxycarbonyl) phenoxy] -3-methoxypropenoic acid methyl; 150.2- {2- [2- (methoxy) Ethoxy) methoxycarbonyl] phenoxy} -3-methoxypropenoate methyl; 151.2- [4-chloro-2- (fluorocarbonyl) phenoxy] -3-
Methyl methoxypropenoate; methyl 152.2- (3-formyl-2-methoxycarbonylphenoxy) -3-methoxypropenoate; methyl 153.2- (3-dibromomethyl-2-carboxyphenoxy) -3-methoxypropenoate Methyl 154.2- (3-bromophthalid-7-yloxy) -3-methoxypropenoate; methyl 155.2- (phthalid-7-yloxy) -3-methoxypropenoate; 156.2- [4-chloro- 2- (methylcarbamoyl) phenoxy] -3-
Methyl 157.2- (2-carboxy-4-chlorophenoxy) -3-ethoxypropionate; 158.2- (2-carboxy-4-chlorophenoxy) -3- (2-trimethyl Methyl fluoromethoxybenzyloxy) propenoate; 159.2- {4-Chloro-2- [N '-(4-fluorophenyl) hydrazinocarbonyl] phenoxy} -3-methoxypropenoic acid methyl; 160.2- {4 -Chloro-2- [N '-(4-methoxyphenyl) hydrazinocarbonyl] phenoxy} -3-methoxypropenoate methyl; 161.2- [2- (2,2,2-trichloroethoxycarbonyl) phenoxy]- Methyl 3-methoxypropenoate; 162.2- [3-fluoro-2- (2,2,2-trifluoroethoxycarbonate) ) Methyl phenoxy] -3-methoxypropenoate; 163.2- [4-Chloro-2- (2,2,2-trifluoroethoxycarbonyl) phenoxy] -3-methoxypropenoic acid methyl; 164.2- [3 Methyl fluoro-2- (2,2,2-trichloroethoxycarbonyl) phenoxy] -3-methoxypropenoate; 165.2- (2-ethylthiocarbonyl-3-fluorophenoxy) -3-
Methyl methoxypropenoate; 166.2- [2- (4-fluorobenzoylmethoxycarbonyl) phenoxy] -3-methyl methyl methoxypropenoate; 167.2- (3-dibromomethyl-2-methoxycarbonylphenoxy)-
Methyl 3-methoxypropenoate.

The numbers 1-167 have been assigned to these compounds for further reference and identification.

Specific examples of the compounds of the general formula (I) provided by the present invention are shown in Tables 1 to 14 below.
These compounds are represented by the general formulas I-2, I-3, I-4, I-5, I-6, I
-7, I-8, I-9, I-10, I-11, I-12, I-13, I-14,
And I-15. Abbreviations used in the tables have the following meanings: M
e means methyl, Et means ethyl, Pr means n-propyl, i
-Pr means isopropyl, c-Pr means cyclopropyl, Bu is n
-Butyl, Pen means pentyl, c-Pen means cyclopentyl, c-Hex means cyclohexyl, Bn means benzyl, Ph
Means phenyl and Ts means tosyl. Also, if there are numbers immediately following an atom or group, these numbers are to be understood as subscripts (eg, CH
3 means CH _3, CH2NO2 means _CH 2 NO _2, etc.).

Furthermore, the compounds of the following ^{table, R 16} to represent one (wherein ^{R 16} represents ^{OR 25)} either Z or E isomers in double bond of formula substituted with (I) And mixtures of both isomers can be represented.

Table 1

[0031]

Embedded image

In the formula (I-2) and the following formula (1-7), R ¹⁰ represents CO ₂ R ³² , R ³² is as defined above, and R ¹⁵ , R ²⁵ , And R ¹⁷ have the meanings indicated below. This can be seen in the following table. Identification Group I is that ^R32 is hydrogen, Na, Me, Et, n-Pr, i-Pr,
c-Pr-methyl, n-Bu, 2-Bu, Pen, c-Pen, c-Hex, B
Individual chemical species representing n, 2-heptyl, octyl, 2-octyl, 2,2,2-trifluoroethyl, 3-chloroprop-1-yl, propargyl, methoxyethyl, ethoxyethyl, allyl. R ¹⁵ groups are represented by (I-2) and (I
-7), arranged in accordance with the numbering scheme, where two or more R ¹⁵ substituents are present, the various meanings are given in the same column.

R^FifteenIs -CR³⁰= NOR³¹, -CR³⁰R²⁹R²⁹¹Or -CR ³⁰ = NNR³⁰R³¹When R represents²⁹, R²⁹¹, R³⁰, And R³¹ Is as defined above.

[0034]

[Table 1]

Table 2

[0036]

Embedded image

In the formulas (I-3 to I-6 and I-8 to I-11), R¹⁰, R^Fifteen, R ²⁵ , And R¹⁷Has the meaning shown in the table. R^FifteenThe base is the formula numbering system
And two or more R^FifteenIf any substituents are present,
The taste is indicated.

R^FifteenIs -CR³⁰= NOR³¹, -CR³⁰R²⁹R²⁹¹Or -CR ³⁰ = NNR³⁰R³¹When R represents²⁹, R²⁹¹, R³⁰, And R³¹ Is as defined above.

[0039]

[Table 2]

Table 3

[0041]

Embedded image

[0042]

[Table 3]

Table 4

[0044]

Embedded image

[0045]

[Table 4]

Table 5

[0047]

Embedded image

[0048]

[Table 5]

Table 6

[0050]

Embedded image

[0051]

[Table 6]

Table 7

[0053]

Embedded image

[0054]

[Table 7]

Table 8

[0056]

Embedded image

[0057]

[Table 8]

Table 9

[0059]

Embedded image

[0060]

[Table 9]

Table 10

[0062]

Embedded image

[0063]

[Table 10]

Table 11

[0065]

Embedded image

In the formula (I-12), p represents 0 or 1, R ¹⁵¹ represents R ¹⁵ or a hydrogen atom, and R ¹⁰ and X ₁ have the following meanings.

[0067]

[Table 11]

Table 12

[0069]

Embedded image

[0070] In this formula (I-13), p represents 0 or ^{1, R 10, R 16,} R 1 5, and _{X 1} have the following meanings. R ¹⁵ groups are arranged according to the numbering scheme (I-13).

[0071]

[Table 12]

Table 13

[0073]

Embedded image

In the formula (I-14), p represents 0 or 1, and R ¹⁰ , R ¹⁵ , and X ₁ have the following meaning. R ¹⁵ groups are arranged according to the numbering scheme (I-14).

[0075]

[Table 13]

Table 14

[0077]

Embedded image

In the formula (I-15), p represents 0, and R ¹⁰ and X ¹ have the following meanings. This can be seen in the following table. In the identification group I, Z is

[0079]

Embedded image Represents an individual chemical species that represents

[0080]

Embedded image Represents a portion to which the rest of the molecule is bonded.

[0081]

[Table 14]

The compounds of formula (I) described above can be synthesized by using or adapting known methods as described below (ie, conventionally used methods or methods described in the literature).

In the following description, if symbols appearing in the formula are not particularly defined, it is to be understood that those symbols are “as defined above” according to the first definition of each symbol in this specification. .

In the following description of the methods, it is to be understood that successive methods can be performed in a different order and that appropriate protecting groups can be required to obtain the desired compound.

According to features of the compounds of the present invention, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁶ ,
R ¹⁷ , p, X ₁ , X ₂ , and X ₃ are as defined above, and R ¹⁰ is -C
Represents O ₂ R ^33, the compound of formula (I) ^{in which R 33} represents ^{R 32} other than hydrogen atoms,
It can be synthesized by reacting the corresponding compound of formula (I), wherein R ¹⁰ represents CO ₂ H, with an alcohol of formula (II): R ³³ —OH (II).

[0086] The reaction is generally an organic solvent, preferably carried out in the presence of an alcohol R ^33, optionally an acid or base catalyst is preferably carried out in the presence of an acid catalyst such as sulfuric acid.

According to a further feature of the present invention, the various symbols are as defined above,^{1 0} Is -CO₂The compound of formula (I) representing H is represented by R¹⁰Is -CO₂R³³And R ³³ From a corresponding compound, which represents t-butyl, in a solvent such as dichloromethane.
Synthesized by using an acid such as trifluoroacetic acid at a temperature of 0 to 50 ° C
can do.

[0088] According to a further feature of the present invention, are as different symbols defined ^above, the compounds of formula (I) ^{in which R 1 0} represents ^-CONR 30 ^{R 31 is} a ^{R 10} is -CO ₂ H Synthesizing the corresponding compound of formula (I) by treating with a halogenating agent to synthesize an acyl halide, followed by treatment with an amine of formula (III): R ³⁰ R ³¹ NH (III) Can be.

The halogenating agent is generally oxalyl halide or sulfonyl halide, and the halide is preferably chloride. The halogenation can be carried out in the presence or absence of a solvent, preferably in a halogenated hydrocarbon such as dichloromethane at a temperature of 0 ° C. to 40 ° C., optionally with dialkylformamide as a catalyst, usually Is carried out in the presence of dimethylformamide. The reaction of the acyl halide thus formed with the amine of formula (III) is generally carried out in an inert solvent such as dichloromethane, optionally in the presence of a base, generally in the presence of a tertiary amine base such as triethylamine. At a temperature between 0 ° C and 40 ° C.

[0090] According to a further feature of the present invention, various symbols are as defined in ^{above, R 1 0} is _{-CH 2 NO 2, -CH 2 SCN} , -CH 2 CN, or _-CH 2 _{N 3} it is a compound of formula (I), R ¹⁰ is -CH 2 -L _(wherein, L is a leaving group, generally a sulfonic acid ester such as p- toluenesulfonate or mesylate) corresponding formula is ( The compound of I), or R ¹⁰ is -CH ₂ -L ¹ (wherein
L ¹ is a leaving group, generally a halogen) and can be synthesized from the corresponding compound of formula (I), each in an organic solvent such as dimethylformamide or dimethylsulfoxide. C. to 150.degree. C., preferably 0.degree.
At a temperature between 60 ° C., with a suitable metal salt of a nitro, thiocyano, cyano or azide anion, in particular a salt of a Group Ia or Group Ib metal, such as sodium, potassium or silver. It can be synthesized by processing. Such compounds are known in the literature or can be synthesized from compounds known by those skilled in the art.

[0091] According to a further feature of the present invention, it is as different symbols defined ^above, the compound of the formula ^{R 1 0} is ^{-C (= NR 35) R 32} (I) ^{is, R 10} is - a corresponding compound of formula (I) is COR ^{3 2,} formula ^(IV); a compound of R ₃₅ NH 2 (IV), optionally, toluene, organic such as an alcohol, such as acetic acid or methanol, and ethanol It can be synthesized by reacting in the presence of a solvent, optionally in the presence of an acid such as p-toluenesulfonic acid as a catalyst, or a base such as sodium acetate. The reaction is generally carried out at a temperature between 0 ° C. and 150 ° C., optionally with physical removal of water (eg, by azeotropic distillation) or with a dehydrating agent such as molecular sieves or titanium tetrachloride. Will be

[0092] According to a further feature of the present invention, various symbols are as defined ^above, the compound of the formula ^{R 1 0} is ^{-CH = CHC (O) OR 32} (I) ^{is, R 10} is halogen Can be synthesized by reacting the corresponding compound of formula (I) with a compound of formula (V): CH ₂ ＣＨCHC (O) OR ³² (V).

The halogen is preferably bromine or iodine. The reaction can be carried out in the absence or presence of a solvent, and the solvent may be organic or aqueous. Generally, a polar aprotic solvent such as N, N-dimethylformamide or a polyether such as glyme is used. . The reaction is usually performed in the presence of a transition metal as a catalyst, usually using palladium such as palladium acetate, optionally a base such as triethylamine, and optionally a trialkylphosphine or triarylphosphine, generally such as triphenylphosphine. The reaction is performed in the presence of another catalyst. The reaction is 0 ° C ~
It is carried out at a temperature of 150 ° C, generally between 50 ° C and 150 ° C.

According to a further feature of the present invention, the various symbols are as defined above,^{1 0} Is -CHR²⁷R²⁸Or -CR²⁷R²⁸R²⁸¹And R²⁷, R^{2 8} , And R²⁸¹Is a compound of formula (I) wherein R is as defined above,²⁷, R ²⁸ , And R²⁸¹C of the corresponding compound in which one or more of
It can be synthesized by logenation. The reaction is generally performed using N-bromosuccinyl
N-halosuccinimide such as amide is used in a solvent such as carbon tetrachloride, optionally
Add a radical initiator such as azobisisobutyronitrile, irradiate light arbitrarily,
It is carried out at a temperature from 20 ° C. to the reflux temperature of the solvent.

According to a further feature of the invention, the formula (I) wherein the various symbols are as defined above.
The compounds of formula (VI) have the corresponding formula (VI)

[0096]

Embedded image Wherein R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , X ₁ and p are as defined above, and a compound of formula (VII)

[0097]

Embedded image (Wherein X ₂ , X ₃ , R ¹⁶ , and R ¹⁷ are as defined above, and L ² is a leaving group such as halogen, and is usually a bromine, chlorine, or iodine group) Can be synthesized by optionally reacting the compound with a compound (in general, an amine such as triethylamine or pyridine, or a metal hydride such as sodium hydride).

[0098] According to a further feature of the present invention, it is as different symbols defined ^{above, R 1 6} represents ^{OR 251,} compounds of formula (I) ^{wherein R 251} represents ^{R 25} other than hydrogen atoms , Formula (VIII);

[0099]

Embedded image Can be synthesized by reacting a compound of formula I with an alkylating agent (to introduce the group R ²⁵¹ being alkyl), which is generally a dialkyl sulfate, such as dimethyl sulfate, or an alkyl halide. And preferably an alkyl iodide such as methyl iodide. The reaction can be performed in the absence or presence of an organic solvent. As the organic solvent, ether such as diethyl ether, or dialkylformamide such as dimethylformamide can be used. And optionally in the presence of a base, which may be an organic base such as a tertiary amine or an inorganic base such as a metal carbonate or metal bicarbonate such as potassium carbonate.

According to a further feature of the present invention, R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ ,
A compound of formula (VIII) wherein R ¹⁷ , X ₁ , X ₂ are as defined above, X ₃ represents CR ¹⁹ and R ¹⁹ represents R ²⁴ is a compound of formula (IX);

[0101]

Embedded image Can be synthesized by reacting the compound with an aminomethylating agent, followed by hydrolysis with an acid. The aminomethylating agent is generally a dialkylaminodialkyl acetal, such as dimethylformamide dimethyl acetal, or an alkoxybis (dialkylamino) methane, especially t-butoxybis (dimethylamino) methane (Bredereck reagent). The reaction is carried out in the absence of an organic solvent or in the presence of an organic solvent such as toluene at 20 ° C to 15 ° C.
It is carried out at a temperature between 0 ° C, preferably at a temperature between 80 ° C and 130 ° C. The hydrolysis is carried out using an acid, generally using a mineral acid such as hydrochloric acid in the presence of an organic solvent,
This organic solvent may or may not be miscible with water, such as tetrahydrofuran.

[0102] According to a further feature of the present invention, are as different symbols defined ^{above, R 1 0} represents -COCH ₂ COR ^33, wherein ^{R 33} is as defined in above (I)
Can be synthesized from the corresponding compound in which R ¹⁰ is replaced by the group COCH (CO ₂ tBu) COR ³³ . The reaction is generally carried out at a temperature between 0 and 50 ° C. using an acid such as 4-toluenesulfonic acid in a solvent such as dichloromethane.

According to a further feature of the present invention, compounds of formula (I) wherein R ¹⁰ represents —COF are prepared at 0-50 ° C. in an inert solvent such as dichloromethane in the presence of a base such as pyridine.
In the above, the compound can be synthesized by reacting a corresponding compound in which R ¹⁰ represents CO ₂ H with a fluorinating agent such as cyanuric fluoride.

[0104] R ¹⁰ represents _-CO 2 ^{R 33, the compound R 33} represents t- ^{butyl, to} a ^{compound R 10} corresponding represents a -CO ₂ H, and in a solvent t- butanol such as dichloromethane reaction Can be synthesized. This reaction is carried out at 0-50 ° C. in the presence of an acid such as sulfuric acid and preferably a dehydrating agent such as anhydrous magnesium sulfate.
At a temperature of

According to a further feature of the invention, the compounds of formula (IX) are of the formula (X)

[0106]

Embedded image (Wherein R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are as defined above, L ³ is a leaving group, generally a sulfonate such as triflate or tosylate, or generally A compound of formula (XI)

[0107]

Embedded image (Wherein X ¹ , X ² and R ¹⁷ are as defined above), optionally in the presence of a base such as a tertiary amine, metal carbonate or metal hydride. Can be synthesized. Compounds of formula (XI) are known from the literature or can be synthesized by known methods.

The intermediate of formula (I) in which R ¹⁰ has been replaced by COCH (CO ₂ tBu) COR ^{33 as} used in the above description comprises the corresponding acid of formula (I) in which R ¹⁰ represents CO ₂ H
Converted to an acid chloride using a chlorinating agent such as oxalyl chloride in an inert solvent,
Subsequently, the compound is synthesized by reacting with a metal salt (preferably a magnesium salt) of a compound of the formula (XII) R ³³ COCH ₂ CO ₂ t-Bu (XII) (wherein R ³³ is as defined above). be able to. This reaction is generally performed in a solvent such as toluene.

Formulas (II), (III), (IV), (V), (VI), (VII), (IX)
), (X), and (XI) are generally known or can be synthesized by known methods.

The following examples are provided to illustrate the present invention and to facilitate those skilled in the art in studying the reproduction of the present invention. However, these examples should not be construed as limiting the invention. Some of the first steps of some embodiments may already be known, directly or indirectly, for analogous compounds. Nevertheless, such statements have been added to the description to provide easier and better ways of carrying out any of the compounds of the invention as one skilled in the art would arrive.

[0111]Example 1  0.396 g of 2- (2-t-butyloxycarbonyl-4-chlorophenoxy)
B) methyl-3-hydroxypropenoate was added to 336 mg of K₂CO₃, (CH₃ )₂SO₄(0.16 ml), and dimethylformamide (8.2 ml)
I combined. The mixture was stirred at 20 ° C. for 12 hours and extracted with ether (Na₂C
O₃After adding). The organic layer was washed with water and brine, then dried and
(2-t-butyloxycarbonyl-4-chlorophenoxy) -3-methoxyprop
Methyl lopenate (compound 1) was obtained. M. S. The result of the analysis was m / z 343 (M +
H).

By performing a similar method, the following compound was synthesized: 2- [2-methoxycarbonyl-3- (2-methyl-1,3-dioxolane-
2-yl) phenoxy] -3-methoxypropenoic acid methyl (Compound 139, NM
R (CDCl ₃ ): 1.75 (s, 3H), 3.70 (s, 3H), 3.85 (
s, 3H), 3.90 (s, 3H), 3.73 (m, 2H), 4.00 (m, 2
H), 6.75 (d, 1H), 7.00 to 7.35 (m, 3H)); and methyl 2- (2-methoxycarbonylbenzyloxy) -3-methoxypropenoate (Compound 140, NMR ( CDCl ₃ ): 3.6 (s, 3H), 3.7 (s
, 3H), 3.8 (s, 3H), 5.2 (s, 2H), 6.95 (s, 1H),
7.25 (t, 1H), 7.5 (t, 1H), 7.8 (d, 1H), 7.9 (d
, 1H)).

[0113]Example 2  298 mg of 2-t-butyloxycarbonyl-4-chlorophenoxy) -3
-Methyl methoxypropenoate with CH₂Cl₂(0.9ml) and CF₃CO
OH (0.67 ml). The mixture was stirred at 20 ° C. for 2 hours,
Diluted with chill, then extracted with aqueous sodium carbonate and then with water. 2 in the water phase
The mixture was acidified by addition of N HCl and extracted with ethyl acetate. Wash and dry the organic layer
Dry and evaporate to give 2- (2-carboxy-4-chlorophenoxy) -3-meth.
Methyl xypropenoate (compound 2, white solid, melting point 119-120 ° C) was obtained.

The following compounds were synthesized analogously: methyl 2- (2-carboxy-4-methylphenoxy) -3-methoxypropenoate (compound 45, melting point 128-130 ° C.); 2- [2-carboxy- Methyl 3- (2-methoxy-1-methoxycarbonylvinyloxy) phenoxy] -3-methoxypropenoate (Compound 46, NMR (
CDCl ₃ ) 3.75 (s, 6H), 3.9 (s, 6H), 6.6 (d, 2H)
, 7.2 (t, 1H), 7.35 (s, 2H)): 2,4-dichlorophenyl 2- (2-carboxy-4-chlorophenoxy)-(3-methoxy) thiopropenoate (Compound 47, M S.m / z 455 (M + N
a + H); 431 (M -H)); 2- (2- carboxy-4-chlorophenoxy) -3- (1-ethoxy) ethoxy propenoate Methyl (Compound _{48, NMR (CDCl 3):} 1.2
5 (t, 3H), 1.5 (d, 3H), 3.7 (s, 3H), 4.2 (q, 2H
), 4.6 (q, 1H), 7.1 (d, 1H), 7.35 (dd, 1H), 7.
4 (s, 1H), 7.85 (d, 1H)); methyl 2- (2-carboxy-4-chlorophenoxy) -3-prop-2-ynyloxypropenoate (Compound 49, NMR (CDCl ₃₎ ): 2.75 (t, 1
H) 3.8 (s, 3H), 4.7 (d, 2H), 6.9 (d, 1H), 7.4
(Dd, 1H), 7.65 (s, 1H), 8.0 (d, 1H), 9.25 (bs
, 1H)); methyl 2- (2-carboxy-4-methoxyphenoxy) -3-methoxypropenoate (Compound 72, NMR (CDCl ₃ ): 3.80 (s, 3H), 3.85
(S, 3H), 4.00 (s, 3H), 6.90 (d, 1H), 7.00 (d,
1H), 7.40 (s, 1H ), 7.55 (s, 1H)); 2- (2- carboxy-4-chlorophenoxy) -3-methoxy-propenoic acid butyl (compound 73, NMR (CDCl ₃₎ 0.90 (t, 3H), 1.30 (m
, 2H), 1.60 (m, 2H), 4.00 (s, 3H), 4.20 (t, 2H)
), 6.90 (d, 1H), 7.40 (d, 1H), 7.45 (s, 1H), 8
. 00 (s, 1H)); methyl 2- (2-carboxy-3-fluorophenoxy) -3-methoxypropenoate (compound 74, melting point 104-106 ° C); 2- (2-carboxy-3-chlorophenoxy) -3-methoxy-propenoic acid methyl (compound 75, mp 151-152 ° C.); 2-(2-carboxy-3-methylphenoxy) -3-methoxy-propenoic acid methyl (compound _{76, NMR (CDCl 3):} 2.4 (S, 3H), 3.7 (s,
3H), 3.9 (s, 3H), 6.7 (d, 1H), 6.9 (d, 1H), 7.
15 (t, 1 H), 7.3 (s, 1 H)); methyl 2- (2-carboxy-4-chlorophenoxy) -3-methylthiopropenoate (Compound 77, NMR (CDCl ₃ ) 2.5 (s , 3H), 3.8 (s,
3H), 6.9 (d, 1H), 7.4 (m, 1H), 7.6 (s, 1H), 8.
0 (d, 1H), OH acid was not observed); 2- (2-carboxy-phenoxy) -3-methoxy-propenoic acid methyl (compound _{78, NMR (CDCl 3):} 3.8 (s, 3H) , 4.0 (s, 3H);
9 (d, 1H), 7.2 (t, 1H), 7.5 (m, 3H), 8.0 (d, 1H)
)); Methyl 2- (1-carboxynaphth-2-yloxy) -3-methoxypropenoate (compound 79, melting point 145.4 ° C); 2- (2-carboxy-3,4-difluorophenoxy) -3- Methyl methoxypropenoate (Compound 80, NMR (CDCl ₃ ): 7.40 (s, 1H), 7
. 18 (q, 1H), 6.70 (dt, 1H), 4.02 (s, 3H), and 3.80 (s, 3H)); 2- (2-carboxy-3-chloro-4-fluoro) Methyl phenoxy) -3-methoxypropenoate (Compound 81, melting point 131 ° C.); Methyl 2- (2-carboxy-4-chloro-3-fluorophenoxy) -3-methoxypropenoate (Compound 82, NMR (CDCl ₃ ) : 3.7 (s, 3H)
, 3.95 (s, 3H), 6.65 (m, 1H), 7.35 to 7.2 (m, 2H)
); 19FNMR-111.834); 2- (2- carboxy-4-difluoromethyl-phenoxy-3-methoxy propenoic acid methyl (compound _{83, NMR (CDCl 3):} 3.8 (s, 3H), 4.
0 (s, 3H), 6.85 to 6.45 (t, 1H), 7.0 (d, 1H), 7.
5 (s, 1H), 7.65 (m, 1H), 8.2 (m, 1H)); methyl 2- (4-bromo-2-carboxyphenoxy) -3-methoxypropenoate (Compound 84, melting point 142.7-145 ° C); methyl 2- (2-carboxy-4-fluorophenoxy) -3-methoxypropenoate (compound 85, melting point 141.5-143.1 ° C); 2- (3-bromo-2) - carboxyphenoxy) -3-methoxy-propenoic acid methyl (compound _{86, NMR (CDCl 3):} 3.75 (s, 3H), 4.0 (s
, 3H), 6.9 (d, 1H), 7.2 (t, 1H), 7.35 to 7.55 (m
, 2H)); 2- (2- carboxy-3-thiocyanato-methylphenoxy) -3-methoxy-propenoic acid methyl (compound _{87, NMR (CDCl 3):} 3.7 (s, 3H),
3.95 (s, 3H), 4.2 (s, 2H), 6.9 (d, 1H), 7.1 (d
, 1H), 7.3~7.5 (d, 2H)); 2- (3- acetoxymethyl-2-carboxy-phenoxy) -3-methoxy-propenoic acid methyl (compound _{88, NMR (CDCl 3):} 2. 1 (s, 3H), 3
. 45 (s, 2H), 3.75 (s, 3H), 4.0 (s, 3H), 6.9 (d
, 1H), 7.15 (d, 1H), 7.35 (t, 1H), 7.4 (s, 1H)
); 2- (2-carboxy-3,4-dichlorophenoxy) -3-methoxy-propenoic acid methyl (compound _{89, NMR (CDCl 3):} 3.7 (s, 3H), 4.0
(S, 3H), 6.8 (d, 1H), 7.4-7.5 (m, 2H)); methyl 2- (2-carboxy-3,4-difluorophenoxy) -3-methoxypropenoate (Compound 115, NMR (CDCl ₃ ): 7.30 (s, 1H),
7.12 (q, 1H), 6.60 (dt, 1H), 3.96 (s, 3H),
90 (s, 3H), and 3.72 (s, 3H)); 2- (2- carboxy-4-chlorophenoxy) -3-ethoxy-propenoic acid methyl (compound _{157, NMR (CDCl 3):} 1.35 (T, 3H), 3.75
(S, 3H), 4.2 (q, 2H), 6.9 (d, 1H), 7.4 (dd, 1H)
), 7.5 (s, 1 H), 7.95 (d, 1 H), 9.4 (bs, 1 H)); and 2- (2-carboxy-4-chlorophenoxy) -3- (2-tri Methyl fluoromethoxybenzyloxy) propenoate (Compound 158, NMR (CDCl ₃ ): 3.75 (s, 3H), 5.25 (s, 2H), 6.85 (d, 1H), 7
. 35 (m, 5H), 7.6 (s, 1H), 7.95 (d, 1H), 8.6 (b
s, 1H)).

[0115]Example 3  Similarly, according to the corresponding series of reactions of Examples 1 and 2 and Reference Examples 3, 4, and 5,
Starting from 5-iodosalicylic acid, 2- (2-carboxy-4-iodopheno)
Methyl xy-3-methoxypropenoate (compound 3, melting point 130-131 ° C.) was obtained.
Was.

[0116]Example 4  5.13 g of 2- (4-chloro-2-methylphenoxy) -3-methoxypro
Methyl penate, 3.56 g of N-bromosuccinimide, and a catalytic amount of azobi
The mixture of isobutyronitrile was heated to reflux in carbon tetrachloride for 4 hours.
Was irradiated. The mixture obtained is filtered through silica gel, the solvent is evaporated and the residual
The product was fractionally recrystallized to give 2- (2-bromomethyl-4-chlorophenoxy) -3
-Methyl methoxypropenoate (NMR (CDCl₃): 3.70 (s, 3H),
3.9 (s, 3H), 4.60 (s, 2H), 6.70 (d, H), 7.20 (
d, 1H), 7.30 (s, 1H), 7.40 (s, 1H)), and 2- (2-di
Methyl bromomethyl-4-chlorophenoxy-3-methoxypropenoate (compound
Compound 4, NMR (CDCl₃): 3.70 (s, 3H), 3.9 (s, 3H), 6
. 70 (d, 1H), 7.20 (d, 3H), 7.30 (s, 2H), 7.90
(S.1H)) was obtained.

[0117]Example 5  100 mg of 2- (2-bromomethyl-4-chlorophenoxy) -3-methoxy
Methyl acrylate is combined with 70 mg of N-methylmorpholine N-oxide monohydrate.
Mix and stir at 20 ° C. for 12 hours in acetonitrile in the presence of sieve as desiccant
Stirred. The mixture was filtered, washed with water and dried, and 56 mg of 2- (
Methyl 2-formyl-4-chlorophenoxy) -3-methoxypropenoate (Compound
Thing 5, M.P. S. m / z 271 (M + H)).

[0118]Example 6  0.1 g of 2- (2-bromomethyl-4-chlorophenoxy) -3-methoxy
Methyl acrylate, 45.3 mg of potassium carbonate, N-methylaniline (35.
5 μl) and toluene (1 ml) were heated at 100 ° C. for 18 hours. Filtered,
Evaporate and chromatograph further to give 2- [4-chloro-2-((N
-Methyl-N-phenylamino) methyl) phenoxy] -3-methoxypropene
Methyl acid (Compound 6, MS m / z 362 (M + H)) was obtained.

The following compounds were similarly synthesized by replacing N-methylaniline with the nitrogen compounds in the table below:

[0120]

[Table 15]

[0121]Example 7  0.1 g of 2- (2-bromomethyl-4-chlorophenoxy) -3-methoxy
Methyl acrylate, 0.068 g of silver nitrite, and diethyl ether (1 ml
) Was stirred at 0 ° C. for 8 hours and then at ambient temperature for 60 hours. Filtered and evaporated
The residue was chromatographed to give 2- (4-chloro-2- (nitro
Methyl) phenoxy) methyl 3-methoxypropenoate (Compound 16, MS
m / z 302 (M + H)).

[0122]Example 8  0.1 g of 2- (2-bromomethyl-4-chlorophenoxy) -3-methoxy
To a mixture of methyl acrylate and DMSO (1 ml) was added 0.021 g of shear at 0 ° C.
Potassium hydride was added. Stir the contents at ambient temperature for 16 hours, then dilute with water
And extracted with diethyl ether. Wash the organic layer with saturated sodium chloride solution
And dried and evaporated to give 2- (4-chloro-2- (cyanomethyl) phenoxy).
B) Methyl 3-methoxypropenoate (Compound 17, MS m / z 282 (M
+ H)).

[0123]Example 9  0.1 g of 2- (2-bromomethylphenoxy) -3-methoxyacrylic acid
0.026 g of sodium thiocyanate at 0 ° C. was added to a mixture of chill and DMSO (1 ml).
Lium was added. Stir the contents at ambient temperature for 16 hours, then dilute with water,
Extracted with ethyl acid. The organic layer is washed with saturated sodium chloride solution, dried
And evaporated to give 2- (4-chloro-2- (thiocyanomethyl) phenoxy) -3
-Methyl methoxypropenoate (Compound 18, MS m / z 314 (M + H))
I got

[0124]Example 10  0.04 g of 2- (2-carboxy-4-chlorophenoxy) -3-methoxy
Methyl propenoate, concentrated H₂SO₄(20 μl) and methanol (3 ml)
Stir at ambient temperature for 18 hours, then at 60 ° C. for 30 minutes. Evaporate the solvent
And the residue was partitioned between diethyl ether and aqueous sodium bicarbonate.
I let you. The organic layer was separated, dried and evaporated to give 0.042 g of 2- (4-k).
Methyl roro-2-methoxycarbonylphenoxy) -3-methoxypropenoate (
Compound 19, NMR (CDCl₃): 3.80 (3H, s), 3.85 (3H, s)
s), 3.60 (3H, s)).

Similarly, using ethanol, methyl 2- (4-chloro-2-ethoxycarbonylphenoxy) -3-methoxypropenoate (Compound 20, NMR (CDCl ₃ ): 3.75 (s, 3H), 1.30 (t, 3H), 3.60 (s, 3H), 4
. 30 (q, 2H) was obtained.

The following compounds were synthesized similarly: Methyl 2- [4-chloro-2- (prop-2-ynyloxycarbonyl) phenoxy] -3-methoxypropenoate (Compound 51, MS m / z325 (M +
H)); methyl 2- [2- (benzyloxycarbonyl) -4-chlorophenoxy] -3-methoxypropenoate (Compound 52, MS m / z 377 (M + H)); 2- [4-chloro- Methyl 2- (propyloxycarbonyl) phenoxy] -3-methoxypropenoate (Compound 53, MS m / z 329 (M + H)); 2- [2- (butyloxycarbonyl) -4-chlorophenoxy] -3 -Methyl methoxypropenoate (Compound 54, MS m / z 343 (M + H)); 2- [4-chloro-2- (prop-2-yloxycarbonyl) phenoxy]
Methyl -3-methoxypropenoate (Compound 55, MS m / z 329 (M + H
)); Methyl 2- [4-chloro-2- (3-chloropropyloxycarbonyl) phenoxy] -3-methoxypropenoate (Compound 56, MS m / z 363 (M +
H)); 2- [4-Chloro-2- (but-2-yloxycarbonyl) phenoxy]-
Methyl 3-methoxypropenoate (Compound 57, MS m / z 343 (M + H)
); 2- [4-chloro-2- (3-pentyloxycarbonyl) phenoxy] -3
-Methyl methoxypropenoate (Compound 58, MS m / z 357 (M + H))
2- [4-chloro-2- (hept-2-yloxycarbonyl) phenoxy]
Methyl -3-methoxypropenoate (Compound 59, MS m / z 385 (M + H
)); Methyl 2- [4-chloro-2- (octyloxycarbonyl) phenoxy] -3-methoxypropenoate (Compound 60, MS m / z 399 (M + H)); -(Cyclopentyloxycarbonyl) phenoxy]-
Methyl 3-methoxypropenoate (Compound 61, MS m / z 355 (M + H)
); 2- [4-chloro-2- (2-methoxyethoxycarbonyl) phenoxy]-
Methyl 3-methoxypropenoate (Compound 62, MS m / z 345 (M + H)
); 2- [4-chloro-2- (2-ethoxyethoxycarbonyl) phenoxy]-
Methyl 3-methoxypropenoate (Compound 63, MS m / z 359 (M + H)
); 2- [4-chloro-2- (cyclopropylmethoxycarbonyl) phenoxy]
Methyl-3-methoxypropenoate (compound 64, MS m / z 341 (M + H
)); Methyl 2- (4-methoxy-2-methoxycarbonylphenoxy) -3-methoxypropenoate (Compound 65, NMR (CDCl ₃ ): 3.70 (s, 3H),
3.80 (s, 3H), 3.85 (s, 3H), 3.90 (s, 3H), 6.8
0 (d, 1H), 6.95 (d, 1H), 7.30 (s, 1H), 7.40 (s)
, 1H)); 2- (4- bromo-2-methoxycarbonyl-phenoxy) -3-methoxy-propenoic acid methyl (compound _{100, NMR (CDCl 3):} 3.70 (s, 3H),
3.85 (s, 3H), 3.9 (s, 3H), 6.8 (d, 1H), 7.30 (
s, 1H), 7.45 (d, 1H), 8.00 (s, 1H)); methyl 2- (4-fluoro-2-methoxycarbonylphenoxy) -3-methoxypropenoate (Compound 101, NMR ( _{CDCl 3): 3.70 (s,} 3H)
, 3.85 (s, 3H), 3.90 (s, 3H), 6.83 (m, 1H), 7.
10 (m, 1H), 7.30 (s, 1H), 7.55 (d, 1H); (19 F)
-122.21 (s, 1F)); and 2- (2-ethoxycarbonyl-3-fluorophenoxy) -3-methoxy-propenoic acid methyl (compound _{102, NMR (CDCl 3) 1.3} (t, 3H), 3
. 6 (s, 3H), 3.8 (s, 3H), 4.35 (q, 2H), 6.6 (d,
1H), 6.7 (t, 1H), 7.2 (m, 1H), 7.25 (s, 1H)).

[0127]Example 11  0.042 g of 2- (2-carboxy-4-chlorophenoxy) -3-methoxy
Methyl cypropenoate and CH₂Cl₂(5 ml), oxalyl chloride (
14.1 μl) and CH of dimethylformamide₂Cl₂Solution (5 ml CH₂C
l₂One drop of DMF) 73 μl was added. Heat the contents at 40 ° C for 1 hour,
On cooling, 0.026 g of 4-trifluoromethoxyaniline and CH₂Cl₂(
0.1 ml) and then triethylamine (44.9 μl).
Was. The reaction mixture is stirred at ambient temperature for 4 hours and then chromatographed.
And purified to give 0.062 g of 2- (4-chloro-2-N- (4-trifluoromethane).
Toxiphenyl) -aminocarbonyl) phenoxy-3-methoxypropenoic acid
Cyl (compound 21, NMR (CDCl₃): 8.0 (broad, 1H), 7.4
0 (s, 1H), 7.15 (d, 2H), 7.70 (d, 2H)).

The following amides were similarly synthesized using the appropriate amines;

[0129]

[Table 16]

The following compounds were similarly synthesized: 2- [2- (benzatriazol-1-yloxycarbonyl) -4-chloro
Methyl phenoxy] -3-methoxypropenoate (Compound 66, MS m / z4
04 (M + H)); 2- [4-chloro-2- (4-nitrophenoxycarbonyl) phenoxy]-
Methyl 3-methoxypropenoate (Compound 67, MS m / z 408 (M + H)
); 2- [4-chloro-2- (2,4,5-trichlorophenoxycarbonyl) phenyl
Enoxy] -3-methoxypropenoate methyl (compound 68, MS m / z 48
2 (M + H)); 2- [4-chloro-2- (2,3,4,5,6-pentachlorophenoxycal)
Bonyl) phenoxy] -3-methoxypropenoic acid methyl (Compound 69, MS
m / z 550 (M + H)); 2- [4-chloro-2- (ethylcarbamoyl) phenoxy] -3-methoxy
Methyl propenoate (Compound 70, MS m / z 314 (M + H)); 2- [4-chloro-2- (ethylthiocarbonyl) phenoxy] -3-methoxy
Methyl cypropenoate (Compound 71, MS m / z 331 (M + H)); 2- {4-chloro-2- [N '-(2-chlorophenyl) hydrazinocarboni
[Phenoxy) -3-methylpropenoate (Compound 50, NMR (CD
Cl₃): 3.75 (s, 3H), 3.95 (s, 3H), 6.65 (d, 1H)
), 6.8 (m, 2H), 7.0 (m, 1H), 7.1 (m, 1H) 7.25 (
m, 2H), 7.4 (s, 1H), 7.95 (d, 1H), 9.5 (m, 1H)
); 2- {4-chloro-2- [N '-(2,4-dichlorophenyl) hydrazinoca]
[Rubonyl] methyl phenoxy} -3-methoxypropenoate (Compound 92, NMR
(CDCl₃): 3.75 (s, 3H), 4.0 (s, 3H), 6.65 (d,
1H), 6.85 (d, 1H), 6.95 (d, 1H), 7.1 (dd, 1H)
, 7.35 (m, 2H), 7.4 (s, 1H), 8.0 (d, 1H), 9.7 (
d, 1H)); 2- {4-chloro-2- [N '-(3-trifluoromethylphenyl) hydra
Dinocarbonyl] phenoxy} -3-methoxypropenoate methyl (compound 93,
NMR (CDCl₃): 3.8 (s, 3H), 4.0 (s, 3H), 6.5 (d)
, 1H), 6.85 (d, 1H), 7.15 (m, 3H). 7.35 (m, 2H
), 7.45 (s, 1H), 8.0 (d, 1H), 9.65 (d, 1H)); 2- [2- (2,2,2-trifluoroethoxycarbonyl) phenoxy]-
Methyl 3-methoxypropenoate (Compound 94, NMR (CDCl₃): 3.6 (
s, 3H), 3.8 (s, 3H), 4.6 (q, 2H), 6.85 (d, 1H)
, 7.0 (t, 1H), 7.3 (s, 1H), 7.4 (t, 1H), 7.85 (
d, 1H)); 2- [4-chloro-2- (2,2,2-trichloroethoxycarbonyl) phene
Noxy] -3-methoxypropenoate methyl (compound 95, NMR (CDCl₃)
: 3.7 (s, 3H), 3.85 (s, 3H), 4.95 (s, 2H), 6.8
5 (d, 1H), 7.3 (s, 1H), 7.4 (d, 1H), 7.9 (d, 1H)
)); 2- {4-chloro-2-[(1-hydroxy-2-methylprop-2-yl)]
Carbamoyl] phenoxy} -3-methoxypropenoate methyl (compound 96, N
MR (CDCl₃); 1.35 (s, 6H), 3.70 (s, 2H), 3.75
(S, 3H), 3.95 (s, 3H), 6.80 (d, 1H), 7.29 (d,
1H), 7.40 (s, 1H), 7.90 (s, 1H), 7.95 (bs, 1H)
)); 2- [4-methyl-2- (2,2,2-trifluoroethoxycarbonyl) f
Enoxy] -3-methoxypropenoate (compound 97, NMR (CDCl₃ 3.) 2.30 (s, 3H), 3.70 (s, 3H), 3.90 (s, 3H),
65 (q, 2H), 6.80 (d, 1H), 7.25 (d, 1H), 7.30 (
s, 1H), 7.70 (s, 1H)); 2- (3-fluoro-2-hexylthiocarbonylphenoxy) -3-methoxy
Methyl cypropenoate (Compound 98, MS m / z 371 (M + H)); 2- [4-Fluoro-2- (2-ethoxyethoxycarbonyl) phenoxy]
Methyl -3-methoxypropenoate (Compound 99, NMR (CDCl₃): 1.2
2 (t, 3H), 3.58 (d, 2H), 3.70 (s, 3H), 3.75 (m
, 2H), 3.86 (s, 3H), 4.45 (m, 2H), 6.85 (m, 1H)
), 7.08 (m, 1H), 7.30 (s, 1H), 7.55 (m, 1H);^{1 9} F: -122.30 (s)); 2- [4-chloro-2- (diphenylmethyleneiminooxycarbonyl) phene
Noxy] -3-methoxypropenoate methyl (Compound 128, NMR (CDCl₃ ): 3.65 (s, 3H), 3.80 (s, 3H), 6.75 (d, 1H), 7
. 30 to 7.70 (m, 13H)); 2- [4-chloro-2- (methylcarbamoyl) phenoxy] -3-methoxy
Methyl propenoate (Compound 156, MS m / z 300 (M + H)); 2- {4-chloro-2- [N '-(4-fluorophenyl) hydrazinocarbo]
Nil] phenoxy} -3-methoxypropenoate methyl (compound 159, NMR (
CDCl₃): 3.75 (s, 3H), 4.0 (s, 3H), 6.4 (d, 1H)
), 6.9 (m, 5H), 7.35 (dd, 1H), 7.4 (s, 1H), 8.
0 (d, 1H), 9.6 (d, 1H)); 2- {4-chloro-2- [N '-(4-methoxyphenyl) hydrazinocarbo
Nyl] phenoxy} -3-methoxypropenoate methyl (Compound 160, NMR (
CDCl₃); 3.75 (s, 6H), 3.95 (s. 3H),), 6.85 (
m, H), 7.3 (dd, 1H), 7.45 (s, 1H), 8.0 (d, 1H)
9.6 (bs, 1H); 2- [2- (2,2,2-trichloroethoxycarbonyl) phenoxy] -3
-Methyl methoxypropenoate (compound 161, NMR (CDCl₃): 3.6 (
s, 3H), 3.8 (s, 3H), 4.9 (s, 2H), 6.85 (d, 1H)
, 7.0 (t, 1H), 7.3 (s, 1H), 7.4 (t, 1H), 7.9 (d
, 1H)); 2- [3-fluoro-2- (2,2,2-trifluoroethoxycarbonyl)
Methyl phenoxy] -3-methoxypropenoate (Compound 162, NMR (CDC
l₃): 3.6 (s, 3H), 3.8 (s, 3H), 4.6 (q, 2H), 6.
6 (d, 1H), 6.7 (t, 1H), 7.25 (m, 2H)); 2- [4-chloro-2- (2,2,2-trifluoroethoxycarbonyl) phenyl
Enoxy] -3-methoxypropenoate methyl (compound 163, NMR (CDCl ₃ ): 3.7 (s, 3H), 3.85 (s, 3H), 6.85 (d, 1H), 7
. 3- (s, 1H), 7.4 (d, 1H), 7.85 (d, 1H)); 2- [3-fluoro-2- (2,2,2-trichloroethoxycarbonyl) phenyl
Enoxy] -3-methoxypropenoate methyl (compound 164, MS m / z 4
01/403/405 (M + H)); and 2- (2-ethylthiocarbonyl-3-fluorophenoxy) -3-methoxy
Methyl propenoate (compound 165, m / z 315 (M + H)⁺).

[0131]Example 12  0.1 g of 2- (2-formyl-4-chlorophenoxy) -3-methoxypro
Methyl penate was suspended in ethanol (2 ml), and 0.033 g of acetohydra was suspended.
Zid was added. The mixture was stirred at ambient temperature for 18 hours. Filter the precipitate and filter
Washed with an amount of ethanol, dried and dried with 2- (4-chloro-2-acetylamino).
Methyl iminomethylenephenoxy) -3-propenoate (Compound 35, MS m
/ Z327 (M + H)).

In a similar manner, the following compounds were synthesized from the following reactants:

[0133]

[Table 17]

The following compounds were synthesized in a similar manner from the corresponding hydrazine in the presence of sodium acetate: Methyl 2- [2- (pyrid-2-ylhydrazonomethylene) phenoxy] -3-methoxypropenoate ( Compound 130, NMR (CDCl ₃ ): 8.34 (s,
1H), 8.28 (s, 1H), 8.14 (d, 1H), 8.04 (d, 2H)
, 7.60 (t, 1H), 7.38 (d, 1H), 7.36 (s, 1H),
22 (t, 1H), 7.06 (t, 1H), 6.82 to 6.72 (m, 2H),
3.90 (s, 3H), and 3.74 (s, 3H)); methyl 2- [4-chloro-2- (N-methylsulfonylhydrazonomethylene) phenoxy] -3-methoxypropenoate (Compound 131) , MS m / z 363
/ 365 (M + H)); methyl 2- [4-chloro-2- (2,4,6-trichlorophenylhydrazonomethylene) phenoxy] -3-methoxypropenoate (Compound 132, MS m.
/ Z463 / 465/467 (M + H)); methyl 2- {4-chloro-2- [N- (4-morpholinyl) iminomethylene] phenoxy} -3-methoxypropenoate (Compound 133, MS m / z355
/ 357 (M + H)); methyl 2- [4-chloro-2- (pyrid-2-ylhydrazonomethylene) phenoxy] -3-methoxypropenoate (Compound 134, MS m / z 362/3)
64 (M + H)); methyl 2- [4-chloro-2- (4-fluorophenylhydrazonomethylene) phenoxy] -3-methoxypropenoate (Compound 135, MS m / z 379)
/ 381 (M + H)); methyl 2- [4-chloro-2- (4-nitrophenylhydrazonomethylene) phenoxy] -3-methoxypropenoate (Compound 136, MS m / z 406 /
408 (M + H)); and methyl 2- {4-chloro-2- [N- (dimethylthiocarbamoyl) hydrazonomethylene] phenoxy} -3-methoxypropenoate (Compound 137, MS
m / z 372/374 (M + H)).

[0135]Example 13  42 mg of 2- (2-carboxy-4-chlorophenoxy) -3-methoxyprop
Methyl lopenate was dissolved in diethyl ether (0.8 ml) and tetrahydrofuran (0.
4%), and 60% sodium hydride was dispersed in mineral oil.
Was added to 7.5 mg of the resulting dispersion. The mixture was stirred at ambient temperature for 4 hours, resulting in a white precipitate.
A precipitate formed which was filtered, washed with ether, dried and dried to give 2- (2-carbo).
Sodium salt of methyl (xy-4-chlorophenoxy) -3-methoxypropenoate
(Compound 43, melting point 230-234 ° C (decomposition)) was obtained.

By the same method, sodium salt of methyl 2- (2-carboxy-4-iodophenoxy) -3-methoxypropenoate (compound 116, melting point: 234 to 235 ° C.) was synthesized.

[0137]Example 14  50 mg of 2- (2-bromo-4-chlorophenoxy) -3-methoxyprop
Methylate, 30 μl of triethylamine, 3.4 mg of triphenylphosphine
, 40 μl of methyl acrylate, 1.4 mg of palladium acetate, and DMF
(2 ml) was stirred at 100 ° C. for 24 hours. The reaction mixture is treated with 2N HCl.
The mixture was extracted with ethyl acetate, dried and concentrated. To column chromatography
2- (4-chloro-2- (2-methoxycarbonylethenyl) phenoxy
) -3-Methoxypropenoate (Compound 44, MS m / z 327 (M +
H)).

[0138]Example 15  Proceeding according to Example 2, 2- (2-t-butoxycarbonyl-3-forme
Starting from methyl phenoxy) -3-methoxypropenoate, 2- (2-ca)
Methoxy (ruboxy-3-dihydroxymethylphenoxy) -3-methoxypropenoate
(Compound 90, NMR (CDCl₃): 3.6 (s, 3H), 3.8 (s, 3H)
H), 6.5 (s, 1H), 6.85 (d, 1H), 7.15 (d, 1H), 7
. 3 (s, 1H), 7.5 (d, 1H)) and 2- (3-hydroxyphthalide-7)
-Yloxy) -3-methoxypropenoic acid methyl compound (Compound 91, NMR (CDC
l₃): 3.6 (s, 3H), 3.8 (s, 3H), 6.4 (s, 1H), 6.
8 (d, 1H), 7.0 (d, 1H), 7.3 (s, 1H), 7.5 (t, 1H)
)) Was synthesized.

[0139]Example 16  2- (2-carboxy-3-fluorophenoxy) -3-methoxypropenoic acid
Methyl (0.05 g), propargyl bromide (0.278 mmol), and carbonic acid
The mixture of potassium was stirred in acetonitrile while heating to 70 ° C. for 4 hours.
The mixture was cooled and water was added, which was extracted (ether), dried and evaporated,
2- [3-fluoro-2- (prop-2-ynyloxycarbonyl) phenoxy
Methyl 3-methoxypropenoate (Compound 103, 0.047 g, MS m.
/ Z 309 (M + H)).

The following compounds were synthesized by a similar method: Methyl 2- (2-benzyloxycarbonyl-3-fluorophenoxy) -3-methoxypropenoate (Compound 104, MS m / z 361 (M + H) ); 2- [3-fluoro-2- (2-methoxyethoxycarbonyl) phenoxy]
Methyl -3-methoxypropenoate (Compound 105, MS m / z 329 (M +
H)); 2- [2- (2-ethoxyethoxycarbonyl) -3-fluorophenoxy]
Methyl -3-methoxypropenoate (Compound 106, MS m / z 343 (M +
H)); Methyl 2- [3-fluoro-2- (tetrahydrofuran-2-ylmethoxycarbonyl) phenoxy] -3-methoxypropenoate (Compound 107, MSm
/ Z355 (M + H)); methyl 2- [2- (3-chloropropyloxycarbonyl) -3-fluorophenoxy] -3-methoxypropenoate (Compound 108, MS m / z 347 /
349 (M + H)); 2- (2- butyloxycarbonyl-phenoxy) -3-methoxy-propenoic acid methyl (compound _{109, NMR (CDCl 3):} 0.9 (t, 3H), 1.4 (m
, 2H), 1.65 (m, 2H), 3.6 (s, 3H), 3.8 (s, 3H),
4.25 (t, 2H), 6.8 (d, 1H), 7.0 (t, 1H), 7.2 (s
, 1H), 7.3 (t, 1H), 7.75 (d, 1H)); 2- (2- pentyloxycarbonyl phenoxy) -3-methoxy-propenoic acid methyl (compound 110, NMR (CDCl _3): 0.9 (t, 3H), 1.4 (
m, 4H), 1.75 (m, 2H), 3.7 (s, 3H), 3.9 (s, 3H)
, 4.3 (t, 2H), 6.85 (d, 1H), 7.0 (t, 1H), 7.3 (
s, 1H), 7.4 (t , 1H), 7.85 (d, 1H)); 2- (2- octyloxycarbonyl phenoxy) -3-methoxy-propenoic acid methyl (compound 111, NMR (CDCl ₃₎ : 0.9 (t, 3H), 1.3 (
m, 6H), 1.8 (m, 4H), 3.2 (t, 2H), 3.7 (s, 3H),
3.9 (s, 3H), 4.3 (t, 2H), 7.15 (m, 1H), 7.3 (m
, 2H), 7.6 (m, 1H), 7.7 (d, 1H)); methyl 2- [2- (3-chloropropyloxycarbonyl) phenoxy] -3-methoxypropenoate (Compound 112, NMR (CDCl ₃ ): 2.2 (t, 2
H), 3.7 (t, 2H), 3.75 (s, 3H), 3.9 (s, 3H), 4.
5 (t, 2H), 7.2 (d, 1H), 7.35 (m, 2H), 7.6 (m, 1
H), 7.7 (d, 1H )); 2- [2- ( prop-2-Lee sulfonyloxy) phenoxy] -3-methoxy-propenoic acid methyl (compound _{113, NMR (CDCl 3):} 2.5 (T, 1
H), 3.7 (s, 3H), 3.9 (s, 3H), 4.9 (d, 2H), 6.9
(D, 1H), 7.1 (t, 1H), 7.3 (s, 1H), 7.4 (m, 1H)
, 7.9 (d, 1H)) ; and 2- (2-benzyloxycarbonylamino-phenoxy) -3-methoxy-propenoic acid methyl (compound _{114, NMR (CDCl 3):} 3.7 (s, 3H), 3. 9 (
s, 3H), 5.4 (s, 2H), 6.9 (d, 1H), 7.0 (t, 1H),
7.4 (m, 7H), 7.9 (d, 1H)).

[0141]Example 17  N, N-dimethylformamide solution of 4-methylbenzyl bromide (0.05 g)
To a suspension of potassium fluoride (0.034 g) in N, N-dimethylformamide.
added. 2- (2-carboxy-3-methylphenoxy) -3-methoxyprope
A solution of methyl phosphate (0.1 g) in N, N-dimethylformamide was added.
Stirred overnight. Water and ethyl acetate are added and the organic phase is dried (magnesium sulfate).
Um), evaporated to give 2- [3-methyl-2- (4-methylbenzyloxy)
Bonyl) phenoxy] -3-methoxypropenoic acid methyl (Compound 117, 0.1
g, NMR (CDCl₃): 2.25 (s, 3H), 2.35 (s, 3H), 3
. 65 (s, 3H), 3.8 (s, 3H), 5.35 (s, 2H), 6.6 (d
, 1H), 6.8 (d, 1H), 7.1-7.2 (m, 3H), 7.25-7.
4 (m, 3H)).

By the same method, the following compound was synthesized: 2- [2- (2-ethoxyethoxycarbonyl) -3,4-difluoropheno
Xy] -3-methoxypropenoate (Compound 118, NMR (CDCl₃)
: 1.2 (t, 3H), 3.55 (q, 2H), 3.7 (s, 3H), 3.75
(T, 2H), 3.8 (s, 3H), 4.5 (t, 2H), 6.6 (d, 1H)
, 7.1 (q, 1H), 7.25 (s, 1H)); 2- [3,4-difluoro-2- (4-methylbenzyloxycarbonyl) phenyl
Enoxy] -3-methoxypropenoate methyl (Compound 119, NMR (CDCl ₃ ): 2.4 (s, 3H), 3.65 (s, 3H), 3.85 (s, 3H), 6
. 6 (d, 1H), 7.0-7.2 (m, 3H), 7.25-7.4 (m, 3H
)); 2- (2-benzyloxycarbonyl-3,4-difluorophenoxy) -3
-Methyl methoxypropenoate (Compound 120, NMR (CDCl₃): 3.6 (
s, 3H), 3.7 (s, 3H), 5.3 (s, 2H), 6.5 (dd, 1H)
, 7.0 (q, 1H), 7.1 to 7.4 (m, 6H)); 2- [2- (4-methylbenzoylmethoxycarbonyl) phenoxy] -3-
Methyl methoxypropenoate (Compound 121, NMR (CDCl₃): 2.45 (
s, 3H), 3.7 (s, 3H), 3.85 (s, 3H), 5.5 (s, 2H)
, 6.9 (d, 1H), 7.1 (t, 3H), 7.2 to 7.3 (m, 3H), 7
. 45 (t, 1H), 7.85 (d, 2H), 8.05 (d, 1H)); 2- [4-fluoro-2- (4-methylbenzoylmethoxycarbonyl)
Noxy] -3-methoxypropenoate methyl (Compound 122, NMR (CDCl₃ ): 2.37 (s, 3H), 3.65 (s, 3H), 3.80 (s, 3H), 5
. 45 (s, 2H), 6.80 (m, 1H), 7.05 (m, 1H), 7.20
(M, 2H), 7.25 (s, 1H), 7.65 (m, 1H), 7.80 (m,
2H);¹⁹F: -122.08 (s)); 2- [2- (4-nitrobenzoylmethoxycarbonyl) phenoxy] -3-
Methyl methoxypropenoate (Compound 123, NMR (CDCl₃): 8.34 (
d, 2H), 8.14 (d, 2H), 8.00 (d, 1H), 7.44 (t, 1
H), 7.28 (s, 1H), 7.06 (t, 1H), 6.90 (d, 1H),
5.50 (s, 2H), 3.88 (s, 3H), and 3.70 (s, 3H))
2- [2- (3,4-dichlorobenzoylmethoxycarbonyl) phenoxy]
Methyl -3-methoxypropenoate (Compound 124, NMR (CDCl₃): 8.
06 (s, 1H), 8.00 (d, 1H), 7.80 (d, 1H), 7.58 (
d, 1H), 7.44 (t, 1H), 7.34 (s, 1H), 7.08 (t, 1H).
H), 6.90 (d, 1H), 5.44 (s, 2H), 3.86 (s, 3H),
And 3.72 (s, 3H)); 2- [2- (4-cyanobenzoylmethoxycarbonyl) phenoxy] -3-
Methyl methoxypropenoate (Compound 125, NMR (CDCl₃): 8.08 (
d, 2H), 8.00 (d, 1H), 7.80 (d, 2H), 7.44 (t, 1
H), 7.34 (s, 1H), 7.18 (t, 2H), 7.08 (t, 1H),
6.90 (d, 1H), 5.48 (s, 2H), 3.88 (s, 3H), and
3.74 (s, 3H)); 2- [4-chloro-2- (benzoylmethoxycarbonyl) phenoxy] -3
-Methyl methoxypropenoate (Compound 126, NMR (CDCl₃): 7.96
(D, 1H), 7.90 (d, 2H), 7.54 (t, 1H), 7.42 (t,
2H), 7.30 (dd, 1H), 7.26 (s, 1H), 6.68 (d, 1H)
), 5.48 (s, 2H), 3.78 (s, 3H), and 3.64 (s, 3H).
)); 2- [2- (benzoylmethoxycarbonyl) phenoxy] -3-methoxy
Methyl lopenate (Compound 127, NMR (CDCl₃): 7.98 (d, 1H)
, 7.92 (d, 2H), 7.56 (t, 1H), 7.42 (t, 2H), 7.
36 (t, 1H), 7.28 (s, 1H), 7.02 (t, 1H), 6.76 (
d, 1H), 5.48 (s, 2H), 3.80 (s, 3H), and 3.62 (
s, 3H)); and 2- [2- (4-fluorobenzoylmethoxycarbonyl) phenoxy] -3
-Methyl methoxypropenoate (Compound 166, NMR (CDCl₃): 8.08
-7.96 (m, 3H), 7.44 (t, 1H), 7.34 (s, 1H), 7.
18 (t, 2H), 7.08 (t, 1H), 6.90 (d, 1H), 5.50 (
s, 2H), 3.88 (s, 3H), and 3.70 (s, 3H)).

[0143]Example 18  2- [2- (2-t-butoxycarbonyl-3-cyclopropyl-3-oxo
From methyl propanoyl) -4-chlorophenoxy] -3-methoxypropenoate
Except for starting, using the method of Example 2, 2- [4-chloro-2- (
3-cyclopropyl-3-oxopropanoyl) phenoxy] -3-methoxy
Methyl lopenate (Compound 129, NMR (CDCl₃): 0.95 (m, 2H)
, 1.20 (m, 2H), 1.80 (m, 1H), 3.75 (s, 3H),
90 (s, 3H), 6.70 (s, 1H), 6.80 (d, 1H), 7.3 (m
, 1H), 7.40 (s, 1H), 7.90 (d, 1H), 16.25 (s, 1)
H)) was synthesized.

[0144]Example 19  Methyl 2- (4-chloro-2-formylphenoxy) -3-methoxypropenoate
(0.1 g) in a dichloromethane solution was added with ethane-1,2-dithiol (0.0 g).
5 ml) and then boron trifluoride etherate (0.01 ml)
Stirred overnight. Sodium carbonate solution is added, the mixture is stirred and the organic phase is separated.
Dry (magnesium sulfate) and evaporate to give 2- [4-chloro-2- (1,3-
Methyl dithiolan-2-yl) phenoxy] -3-methoxypropenoate (compound
138, 0.1 g, m / z 347/349 (M + H)).

[0145]Example 20  2- [2-methoxycarbonyl-3- (2-methyl-1,3-dioxolane-
2-yl) phenoxy] -3-methoxypropenoic acid methyl (0.31 g) and 4
Refluxing a mixture of toluenesulfonic acid monohydrate (34 mg) and acetone overnight
Stirred. Further, 4-toluenesulfonic acid (17 mg) was added, and after refluxing for 4 hours,
The mixture was evaporated, extracted (ethyl acetate), washed (sodium carbonate solution),
Dry (sodium sulfate), evaporate and crystallize (methanol aqueous solution), 2
-(3-acetyl-2-methoxycarbonylphenoxy) -3-methoxyprope
Methyl ester (compound 141, 0.12 g, NMR (CDCl₃): 2.57 (s
, 3H), 3.72 (s, 3H), 3.85 (s, 3H), 3.95 (s, 3H)
), 7.02 (d, 1H), 7.32-7.50 (m, 3H) NMR (CDCl
3) 2.57 (s, 3H), 3.72 (s, 3H), 3.85 (s, 3H), 3
. 95 (s, 3H), 7.02 (d, 1H), 7.32 to 7.50 (m, 3H)
) Got.

[0146]Example 21  Methyl 2- (4-chloro-2-formylphenoxy) -3-methoxypropenoate
(0.1 g) in toluene while stirring.
. 112 ml of a 3M solution) was added dropwise. After 1 hour, the solvent is evaporated and the residue
Was partitioned between hydrochloric acid (2M) and ethyl acetate. Dry the organic phase (magnesium sulfate
Nesium), evaporated and chromatographed on silica gel with ethyl acetate
/ Toluene (1: 9) and purified by 2- [4-chloro-2- (1-hydrido).
Roxyethyl) phenoxy] -3-methoxypropenoate methyl (compound 142,
24 mg, NMR (CDCl₃): 1.50 (d, 3H), 3.70 (s, 3H)
), 3.90 (s, 3H), 5.30 (m, 1H), 6.70 (d, 1H), 7
. 10 (d, 1H), 7.35 (s, 1H), 7.40 (s, 1H) NMR (C
DCI₃) 1.50 (d, 3H), 3.70 (s, 3H), 3.90 (s, 3H)
), 5.30 (m, 1H), 6.70 (d, 1H), 7.10 (d, 1H), 7
. 35 (s, 1H), 7.40 (s, 1H)).

[0147]Example 22  Oxalyl chloride (0.4 ml) and N, N-dimethylformamide were added to 2- (2
Methyl-carboxy-4-chlorophenoxy) -3-methoxypropenoate (1.
0 g) in dichloromethane and stirred at reflux for 2 hours before evaporation. this
A solution of the residue in tetrahydrofuran was added to trimethylsilyldiazomethane (2M hexane).
2.2 ml of sun solution and tetrahydrofuran of triethylamine (0.6 ml)
The solution was added dropwise at 0 ° C. The mixture was kept at 0 ° C. overnight, then evaporated,
Partitioned between sodium bicarbonate solution and ethyl acetate. Wash the organic phase (water
), Dried (magnesium sulfate) and evaporated to give 2- [4-chloro-2- (dia
Methyl zoacetyl) phenoxy] -3-methoxypropenoate (compounds 143, 1
. 08 g, NMR (CDCl₃): 3.75 (s, 3H), 3.90 (s, 3H)
), 6.55 (s, 1H), 6.80 (d, 1H), 7.30 (d, 1H), 7
. 40 (m, 1H), 7.85 (s, 1H)).

[0148]Example 23  2- (2-carboxy-4-iodophenoxy) -3-methoxypropenoic acid
Dissolve chill (0.15 mmol) in sodium carbonate solution (0.45 mmol)
To the solution was added 3-acetamidophenylboronic acid (67 mg). Para-acetate
Di (II) (catalytic amount) was added and the mixture was stirred overnight at 20 ° C. under nitrogen atmosphere.
did. The resulting mixture was diluted (water), acidified, extracted (dichloromethane),
Dry (magnesium sulfate) and evaporate to give 2- [4- (3-acetamidophene).
Nyl) -2-carboxyphenoxy] -3-methoxypropenoic acid methyl (compound
144, 7 mg, NMR (CDCl₃): 2.2 (s, 3H), 3.8 (s, 3)
H), 4.0 (s, 3H), 7.0 (d, 1H), 7.6-7.25 (m, 6H
), 8.2 (s.1H)).

By the same method, the following compound was synthesized: 2- {2-carboxy-4- [3-fluoro-4-phenyl] phenylpheno
Methyl xyl-3-methoxypropenoate (Compound 145, NMR (CDCl₃)
: 3.8 (s, 3H), 4.0 (s, 3H), 7.05 (d, 1H), 7.65
-7.35 (m, 9H), 7.75 (m, 1H), 8.35 (m, 1H)); 2- [2-carboxy-4- (naphth-2-yl) phenoxy] -3-. Methoki
Methyl cypropenoate (Compound 146, NMR (CDCl₃): 3.75 (s, 3
H), 3.95 (s, 3H), 7.0 (d, 1H), 7.45 (m, 3H), 7
. 9-7.6 (m, 5H), 8.0 (m, 1H), 8.4 (m, 1H)); 2- [4- (4-benzyloxyphenyl) -2-carboxyphenoxy]-
Methyl 3-methoxypropenoate (Compound 147, NMR (CDCl₃): 3.8
(S, 3H), 4.0 (s, 3H), 5.1 (s, 2H), 7.15 to 7.95
(M, 3H), 7.5-7.3 (m, 8H), 7.6 (m, 1H), 8.25 (
d, 1H)); and 2- [2-carboxy-4- (benzo-1,3-dioxolan-5-yl) phenyl
Enoxy] -3-methoxypropenoic acid methyl (compound 148, NMR CDCl ₃ ): 3.8 (s, 3H), 4.0 (s, 3H), 6.0 (s, 2H), 6.8
5 (d, 1H), 7.05 to 6.95 (m, 3H), 7.45 (s, 1H), 7
. 6 (m, 1H), 8.2 (m, 1H)).

[0150]Example 24  Use potassium t-butoxide instead of potassium carbonate and use ether
The following compounds were synthesized by the procedure of Example 16 except that
: 2- [4-chloro-2- (methoxymethoxycarbonyl) phenoxy] -3-
Methyl methoxypropenoate (Compound 149, NMR (CDCl₃): 7.80 (
d, 2H), 7.28 (dd, 1H). 7.26 (s, 1H), 6.76 (d,
1H), 5.40 (s, 2H), 3.80 (s, 3H), 3.64 (s, 3H)
And 3.48 (s, 3H)); and 2- {2- [2- (methoxyethoxy) methoxycarbonyl] phenoxy}-
Methyl 3-methoxypropenoate (Compound 150, NMR (CDCl₃): 7.8
6 (d, 2H), 7.34 (t, 1H), 7.26 (s, 1H), 6.98 (t
, 1H), 6.82 (d, 1H), 5.50 (s, 2H), 3.86-3.78.
(M, 2H), 3.78 (s, 3H), 3.64 (s, 3H), 3.58-3.
50 (m, 2H), and 3.32 (s, 3H)).

[0151]Example 25  Cyanuric fluoride (39.6 mg) and pyridine (11.6 mg) were added to 2- (2-
Methyl carboxy-4-chlorophenoxy) -3-methoxypropenoate (42m
g) in dichloromethane solution and stirred at 20 ° C. for 4 hours under a nitrogen atmosphere. solid
The filtrate is washed (water), dried (magnesium sulfate) and evaporated.
To give 2- [4-chloro-2- (fluorocarbonyl) phenoxy] -3-methoxy
Methyl cypropenoate (Compound 151, 45 mg, NMR (CDCl₃): 3.7
5 (s, 3H), 3.90 (s, 3H), 6.90 (d, 1H), 7.40 (s
, 1H), 7.50 (d, 1H), 7.95 (s, 1H);¹⁹FNMR 10
. 44 (s, 1F)).

[0152]Example 26  2- (3-bromomethyl-2-methoxycarbonylphenoxy) -3-methoxy
Methyl cypropenoate (0.15 g), N-methylmorpholine N-oxide (0.
1g), and a mixture of 4A molecular sieves was added to acetonitrile to finish.
Stirred overnight, filtered and added ethyl acetate and water. Dry the organic phase (magnesium sulfate).
), Evaporated and the residue was chromatographed on silica gel.
Purify by eluting with chlorohexane / ethyl acetate to give 2- (3-formyl-2-methoxy).
Methyl xycarbonylphenoxy) -3-methoxypropenoate (compound 152,
0.045 mg, NMR (CDCl₃): 3.6 (s, 3H), 3.8 (s, 3H)
H), 3.95 (s, 3H), 7.05 (d, 1H), 7.25 (s, 1H),
7.4-7.5 (m, 2H)).

[0153]Example 27  According to the procedure of Example 4, 2- (2-t-butoxycarbonyl-3-methylphen)
Starting from methyl nonoxy) -3-methoxypropenoate, 2- (3-dibromomethyl-2-carboxyphenoxy) -3-methoxypro
Methyl penate (compound 153, NMR (CDCl₃): 3.65 (s, 3H),
3.75 (s, 3H), 6.8 (d, 1H), 7.1 (d, 1H), 7.25 (
s, 1H), 7.5 (s, 1H), 7.55 (t, 1H)); and 2- (3-dibromomethyl-2-methoxycarbonylphenoxy) -3-methoate
Methyl xypropenoate (compound 167, NMR (CDCl₃): 3.65 (s,
3H), 3.8 (s, 3H), 3.9 (s, 3H), 6.7 (d, 1H), 6.
8 (s, 1H), 7.2 (s, 1H), 7.3 (t, 1H), 7.6 (d, 1H)
)) Were similarly synthesized.

[0154]Example 28  Starting from methyl 2- (phthalid-7-yloxy) -3-methoxypropenoate
Except for using the method of Example 4 except that
Methyl yloxy) -3-methoxypropenoate (Compound 154, NMR (CDC
l₃): 3.65 (s, 3H), 3.85 (s, 3H), 6.85 (d, 1H)
, 7.1 (d, 1H), 7.25-7.35 (m, 2H), 7.5 (t, 1H)
) Was synthesized.

[0155]Example 29  2- (2-t-butoxycarbonyl-3-methylphenoxy) -3-methoxy
Using the method of Example 4 except starting from methyl propenoate, 2- (
Methyl phthalide-7-yloxy) -3-methoxypropenoate (Compound 155,
NMR (CDCl₃): 3.7 (s, 3H), 3.85 (s, 3H), 5.25
(S, 2H), 6.8 (d, 1H), 7.05 (d, 1H), 7.4 (s, 1H)
), 7.55 (t, 1H)).

[0156]Reference Example 1  According to the procedure of Example 1, 2- (4-chloro-2-methylphenoxy) -3-h
Methyl droxypropenoate to 2- (4-chloro-2-methylphenoxy) -3
-Methyl methoxypropenoate (MSm / z257 (M + H)) was synthesized,
Methyl-(2-bromo-4-chlorophenoxy) -3-hydroxypropenoate
Methyl 2- (2-bromo-4-chlorophenoxy) -3-methoxypropenoate
(MSm / z321 (M + H)) was synthesized.

[0157]Reference Example 2  2.06 g sodium hydride (60% suspension in mineral oil) and dimethylforma
A mixture of amide (20 ml) was cooled to 0 ° C., and ethyl formate (53.33 m
1) and 12.0 g of methyl (2-bromo-4-chlorophenoxy) acetate and 8
0 ml of a mixture of dimethylformamide was added. Remove the cooling bath and the contents
Was stirred at ambient temperature for 1 hour. Add sodium carbonate solution and add contents with ether
Extracted. Separate the aqueous phase and add HCl_aqAcidify to pH 4 with and extract with ether
Issued. The ether layer is washed with saturated sodium chloride solution, dried, evaporated and
Methyl 2- (2-bromo-4-chlorophenoxy-3-hydroxypropenoate (
M. S. m / z 308 (M + H)).

Starting from methyl (4-chloro-2-methylphenoxy) acetate, methyl 2- (4-chloro-2-methylphenoxy) -3-hydroxypropenoate (MSm / z241 (MH)) was synthesized.

[0159]Reference Example 3  Anhydrous MgSO₄To CH₂Cl₂1.54 m while stirring the suspension
l of concentrated H₂SO₄Was added. After 15 minutes, 5 g of 5-chlorosalicylic acid was added and
Then, t-butanol (13.66 ml) was added. Attach a stopper to the mixture,
Stirred at ambient temperature for 43 hours. Saturated NaHCO is added to this suspension.₃Aqueous solution (220m
l) was added and the resulting mixture was stirred for 20 minutes. The organic phase is separated and
Wash with hexane, dry and evaporate to give tert-butyl 5-chloro-2-hydroxybenzoate.
Chill (NMR (CDCl₃): 11 (1H, s), 7.7 (1H, s), 7.3
5 (1H, d), 6.9 (1H, d), 1.6 (s, 9H)).

[0160]Reference Example 4  To 3.6 g of t-butyl 5-chloro-2-hydroxybenzoate are added 2.2 ml of
Methyl bromoacetate and 4.3 g of K₂CO₃Acetonitrile solution
And heated to reflux for 2.5 hours. The mixture was cooled, diluted with water and extracted with ethyl acetate
Was. The organic layer was washed, dried and treated with (2-t-butyloxycarbonyl-4-
Methyl chlorophenoxy) acetate (NMR (CDCl₃): 7.7 (1H, s),
7.35 (1H, d), 6.8 (1H, d), 4.7 (s, 2H), 3.8 (3
H, s), 1.6 (9H, s)).

In a similar manner, methyl (4-chloro-2-methylphenoxy) acetate (NMR (CDCl ₃ ): 4
. 6 (s, 2H) 3.8 (s), Rf = 0.44 (TLC (silica), Et ₂ O
/ Hexane eluent 1: 1 v / v)) and (2-bromo-4-chlorophenoxy)
Methyl acetate (MS m / z 279 (M + H)) was synthesized.

[0162]Reference Example 5  0.95 g of (2-t-butyloxycarbonyl-4-chlorophenoxy) vinegar
Methyl acid was mixed with 7.5 ml of t-butoxybis (dimethylamino) methane
. The mixture was heated at 80 ° C. for 2 hours, then cooled, diluted with water,₂Cl ₂ Extracted. The organic layer is dried, filtered and purified by chromatography,
2- (2-t-butyloxycarbonyl-4-chlorophenoxy) -3-N-di
Methyl methylaminopropenoate (NMR, 7.7 (1H, s) 7.35 (1H,
d), 7.15 (1H, s), 6.9 (1H, d), 3.6 (3H, s), 3.
0 (s, 6H) 1.6 (9H, s)).

50 mg of 2- (2-t-butyloxycarbonyl-4-chlorophenoxy)
Methyl-3-N-dimethylaminopropenoate was mixed at 0 ° C. with tetrahydrofuran (1.3 ml) and 0.436 ml of aqueous HCl (2M). The mixture was stirred at 20 ° C. for 12 hours, then evaporated, washed with brine and extracted with ether. The organic layer was dried, purified by chromatography, and 2- (2-
Methyl t-butyloxycarbonyl-4-chlorophenoxy) -3-hydroxypropenoate (MSm / z 327 (MH)) was obtained.

[0164]Reference Example 6  Dissolve t-butyl 5-chlorosalicylate (1.6 g) in acetone (35 ml)
And potassium carbonate (4.84 g) and methyl 2-bromo-2-butenoate (1.25
g) was added. The contents were heated to reflux for 24 hours, cooled and filtered. Decompression
And the resulting oil was purified by chromatography to give 2.1 g of
2- (2-t-butyloxycarbonyl-4-chlorophenoxy) but-2-e
Methyl acid salt was obtained. NMR (CDCl₃): 1.6 (s, 9H), 1.75 (d
, 3H), 3.65 (s, 3H), 6.7 (m, 2H), 7.25 (m, 1H)
, 7.70 (m, 1H).

[0165]Reference Example 7  510 mg of 2- (2-t-butyloxycarbonyl-4-chlorophenoxy)
) Methyl but-2-enoate was dissolved in dichloromethane and cooled to -20 <0> C. H
The solution was warmed to ambient temperature by bubbling Cl gas for 5 minutes. After 30 minutes, count the contents
Washed with water and dried. The solvent was removed and 0.41 g of 2- (2-carboxy-4
Methyl (-chlorophenoxy) but-2-enoate was obtained. NMR (CDCl₃):
1.90 (d, 3H), 3.75 (s, 3H), 6.75 (d, 1H) 6.90
(Q, 1H), 7.40 (m, 1H), 8.00 (m, 1H).

[0166]Reference Example 8  130 mg of ethyl 2-chloro-3-oxopropanoate was added to 2 ml of isopropa
And thiosalicylic acid dissolved in 162 μl of triethylamine.
Methyl was added dropwise. Stir contents at ambient temperature for 30 minutes, then at reflux temperature for 3 hours
Stirred. The solvent was removed under reduced pressure and the residue was partitioned between water and ether
. The organic layer was discarded and the aqueous layer was acidified to pH 4 and extracted with ether. That d
Layer was separated, dried, concentrated and purified by column chromatography to give 3
6 mg of 3-oxo-2- (2-methoxycarbonyl) thiophenoxypropane
Ethyl acid (MS m / z 283 (M + H)) was obtained.

11.1 mg of ethyl 3-oxo-2- (2-methoxycarbonyl) thiophenoxypropanoate was dissolved in 0.5 ml of DMF, and dimethyl sulfate (5.6 μl) was dissolved.
Was added, and 11.4 mg of potassium carbonate was further added. 24 hours at ambient temperature
After stirring for 2.5 hours, 2.5 ml of sodium carbonate solution (2N) was added and the contents were extracted with ether. The ether extract was dried and concentrated to give 9.6 mg of 3-
Ethyl methoxy-2- (2-methoxycarbonyl) thiophenyl-2-propenoate was obtained. NMR (CDCl ₃ ): 1.05 (t, 3H), 3.8 (3, 3H)
3.9 (s, 3H), 4.1 (q, 2H), 7.05 (m, 2H), 7.25
(M, 1H), 7.9 (m, 1H) 8.0 (s, 1H).

[0168]Reference Example 9  To dichloromethane containing N, N-dimethylformamide (1 drop)
Methyl rubox-4-chlorophenoxy) -3-methoxypropenoate (1.0 g)
Oxalyl chloride (0.4 ml) was added to the solution of
Stirred. After evaporation, the residue is dissolved in toluene and 3-cyclopropyl-3
Tert-butyl magnesium oxopropanoate methoxide enolate (1.05 g
) Was added and the mixture was stirred overnight. Add hydrochloric acid (2M) and add 5
Stirred for minutes. The organic phase is washed (water), dried (magnesium sulfate) and evaporated
To give 2- [2- (2-t-butoxycarbonyl-3-cyclopropyl-3-
Oxopropanoyl) -4-chlorophenoxy] -3-methoxypropenoic acid
(1.49 g) was obtained.

According to a feature of the present invention, there is provided a method of controlling (suppressing) the growth of a weed (ie, unwanted plant) in a location, the method comprising: Spraying (application) the aryl vinyl ether derivative of (I) or an agriculturally acceptable salt or metal complex thereof. For this purpose, the aryl vinyl ether derivatives according to the invention are usually used in the form of herbicidal compositions (ie in combination with compatible extenders or carriers and / or surfactants suitable for use in herbicidal compositions). Will be described later).

The compounds of formula (I) show herbicidal activity against dicotyledonous (ie broadleaf) and monocotyledonous (eg grass) weeds by pre-emergence and / or post-emergence spraying.

The term “pre-emergence application” means application to the soil in which weed seeds or seedlings are present before the appearance of the weed on the soil surface. The term "post-emergence application" means application to the above-ground or exposed parts of the weeds that have appeared on the soil surface. For example, the compounds of formula (I) are broad-leaved weeds, such as Abutilon theophrasti , Amara
nthus retroflexus , Bidens pilosa , Chen
opodium album , Gallium aparine , Ipomoea
spp. For example, Ipomoea purpurea , Sesbania e
xaltata , Sinapis avensis , Solanum nig
rum , and Xanthium strumarium , and grass weeds such as Alopecurus myosuroides , Av
ena fatua , Digitaria sanguinalis , Echi
nochloa crus-galli , Eleusine indica , and Setaria spp. For example, Setaria faberii or Setaria viridis , and sedges, for example, Cyperus e.
can be used to control the growth of Sculentus .

The amount of the compound of formula (I) to be applied depends on the type of weed, the composition used, the application time,
It depends on the climatic and soil conditions, and on the type of crop (when used to control weed growth in crop growing areas). When applied to crop growing areas, the amount applied should be sufficient to control weed growth without substantially permanent harm to the crop. In general, taking these factors into consideration, good results can be obtained if the applied amount is 1 g to 1000 g of active substance per hectare. However, it should be understood that depending on the particular weed control problem encountered, higher or lower application rates may be used.

The compounds of formula (I) are, for example, cereals such as wheat, barley, oats,
Growing of corn and crops such as rice, soybean, fava beans and beetles, pea, purple coconut palm, cotton, peanut, flax, onion, carrot, cabbage, oilseed rape, sunflower, sugar beet, and permanent grassland or seeded grassland Before or after sowing of crops, or before or after emergence of crops, in areas where weeds are infested in areas that are or will be used for
Pre-emergence or post-emergence spraying by directional or non-directional methods, such as by directional or non-directional spraying, can be used for selective control of weed growth, e. Can be controlled.

The compounds of formula (I) can be used in established orchards and other tree growing areas such as forests,
It can also be used to control the growth of weeds, especially the aforementioned weeds, by spraying them before or after emergence in forests, such as forests and parks, and sugarcane, oil palm and rubber gardens. For this purpose, 50 g to 5000 g, preferably 50 g to 2000 g, most preferably 100 g of active substance per hectare
The compound of formula (I) is applied to weeds before or after planting of trees or plantations by a directional or non-directional method (e.g., directional or non-directional spraying) at application rates between g and 1000 g. Can be sprayed or spread on soil where weeds are expected to appear.

The compounds of formula (I) can also be used for controlling the growth of weeds, especially the aforementioned weeds, in areas where crop control is desired, but not in crop growing areas.

Examples of areas where such crops do not grow include airfields, industrial lands, railway tracks,
These include roadside boundaries, riversides, irrigation or other waterways, shrub lands, and fallow or uncultivated lands, especially where it is desirable to control the growth of weeds to reduce the risk of fire. When used for such purposes, where an overall herbicidal effect is frequently desired, the active compound is usually applied in higher application rates than for the crop-growing areas mentioned above. The exact amount applied will depend on the type of plant being treated and the effect sought.

A directional or non-directional scheme (eg, a directional or non-directional spray)
50 g to 5000 g of active substance per hectare, preferably 50 g to 2000 g
It is particularly suitable for this purpose to carry out the pre-emergence or post-emergence application, preferably the pre-emergence application, at an application rate of g, most preferably 100 g to 1000 g.

When used for controlling weed growth by preemergence spraying, the compounds of formula (I) can be incorporated into soils where weeds are expected to appear. When the compound of formula (I) is used to control weed growth by post-emergence spraying, ie, by spraying the emerged weeds on the aerial or exposed parts, the compounds of formula (I) usually come into contact with the soil. ,
Thereby, it is considered that the effect of pre-emergence control of weeds that germinate late in the soil can also be obtained.

Particularly when long-term control is required, the compound of the formula (I) can be repeatedly applied if necessary.

According to a further feature of the invention, one or more aryl vinyl ethers of the formula (I) or their agriculturally acceptable salts or metal complexes are used in combination therewith, preferably in order to homogeneously disperse the compound. One or more compatible agriculturally acceptable bulking agents (diluents) or carriers and / or surfactants [i.e., of a class generally accepted in the art as suitable for use in herbicidal compositions]. Bulking agents (diluents) or carriers and / or surfactants of the formula (I)
Which is compatible with the compound of the formula (I), and a composition suitable for herbicidal use. The term "uniformly dispersed" includes compositions in which the compound of formula (I) is dissolved in other ingredients. The term "herbicidal composition" is used in a broad sense and includes not only compositions ready for use as herbicides, but also concentrates that need to be diluted before use. Preferably, the composition comprises one or more compounds of formula (I) from 0.05 to 9
0% by weight.

A herbicidal composition can include both a bulking agent or carrier and a surfactant (ie, a wetting agent, dispersing agent, or emulsifying agent). Surfactants which may be added to the herbicidal compositions of the present invention may be ionic or non-ionic and include, for example, sulfolicinoleates, quaternary ammonium derivatives, ethylene oxide and alkylphenols and polyarylphenols ( For example, carboxylic acid esters, sulfuric acid esters and sulfonic acids of anhydrosorbitols which have been made soluble by etherification of free hydroxyl groups by condensation with ethylene oxide, or products mainly comprising condensates with nonylphenol or octylphenol) And alkaline earth metal salts (e.g., dinonyl- and dioctyl-sodium sulfosuccinates), and alkali metal and alkaline earth metal salts of high molecular weight sulfonic acid derivatives (e.g., sodium lignosulfate) Tellurosulfonates and calcium ligno sulfonates, and sodium alkyl benzene sulfonates and calcium alkylbenzene sulphonates) are exemplified.

Suitably, the herbicidal composition according to the invention may comprise up to 10% by weight, for example from 0.05% to 10% by weight, of a surfactant, but if desired, according to the invention. The herbicidal composition may comprise a higher proportion of surfactant, for example up to 15% by weight for liquid emulsified suspension concentrates and up to 25% by weight for liquid water-soluble concentrates.

Examples of suitable solid extenders or carriers include aluminum silicate, particulate silicon dioxide, talc, chalk, calcined magnesia, diatomaceous earth, tricalcium phosphate, cork powder, adsorbent carbon black, and kaolin And clay such as bentonite. The solid compositions, which can be in the form of powders, granules or wettable powders, are prepared either by grinding the compound of formula (I) with a solid filler,
It can be made by impregnating a solution of a compound of formula (I) in a volatile solvent with a solid extender or carrier, evaporating the solvent and, if desired, grinding the product to obtain a powder. preferable. Granules are prepared by adsorbing a compound of formula (I) (dissolved in a suitable solvent, which may be volatile if desired) to a particulate solid extender or carrier and evaporating the solvent if desired, Alternatively, it can be produced by granulating the composition in powder form obtained as described above. Solid herbicidal compositions (particularly wettable powders and granules) can include wetting or dispersing agents (eg, of the type described above) which can also function as bulking agents or carriers when solid.

The liquid compositions according to the invention can take the form of aqueous solutions, organic solutions or aqueous-organic solutions, suspensions and emulsions, which may contain a surfactant.
Suitable liquid extenders when mixed into the liquid composition include water, glycols, glycol ethers, tetrahydrofurfuryl alcohol, acetophenone, cyclohexanone, isophorone, N-alkylpyrrolidones, toluene, xylene, mineral oil, animal oil, Vegetable oils, ester-type vegetable oils, and light aromatic and naphthenic fractions of petroleum (and mixtures of these extenders). The surfactant that can be included in the liquid composition can be ionic or non-ionic (eg, of the type described above) and, in the case of a liquid, can also function as a bulking agent or carrier.

The powders, dispersible granules, and liquid compositions in the form of a concentrate can be diluted with water or other suitable bulking agents, such as mineral or vegetable oils, especially where the bulking agent or carrier is a liquid concentrate. If oil, the composition can be diluted for use.

If desired, the liquid composition of the compound of formula (I) may comprise a self-emulsifying composition comprising the active substance dissolved in an emulsifier which is compatible with the active substance or in a solvent containing the emulsifier. It can be used in the form of an aqueous concentrate, and such a concentrate can be made into a usable composition by simply adding it to water.

Liquid concentrates in which the extender or carrier is an oil can be used without further dilution using electrostatic spraying.

If desired, the herbicidal compositions according to the invention may comprise adhesives, protective colloids, thickeners, penetrants, spreading agents, stabilizers, sequestering agents, anti-caking agents, coloring agents, And conventional auxiliaries such as corrosion inhibitors. These adjuvants can also function as carriers or extenders.

Unless otherwise specified, the following percentages are by weight. Preferred herbicidal compositions according to the invention comprise from 10 to 70% of one or more compounds of formula (I), from 2 to 10% of a surfactant, from 0.1 to 5% of a thickener, from 15 to 15%. Aqueous suspension concentrate containing 87.9% water, 10-90% of one or more compounds of formula (I), 2-10% surfactant, and 8-88% solid extender Or a wettable powder comprising a carrier; water-soluble or water comprising 10-90% of one or more compounds of formula (I), 2-40% sodium carbonate and 0-88% of a solid extender. Dispersible powder, 5 to 50%, for example 10 to 30%, of one or more compounds of the formula (I);
A liquid water-soluble concentrate comprising 5% of a surfactant and 10-90%, for example 45-85% of a water-miscible solvent (eg triethylene glycol) or a mixture of a water-miscible solvent and water, 10-70 % Of one or more compounds of formula (I), 5 to 15% of a surfactant, 0.1 to 5% of a thickener, and 10 to 84.9% of an organic solvent (for example, mineral oil). A liquid emulsifiable suspension concentrate comprising: 1-90%, for example 25-75%, of one or more compounds of formula (I);
It contains 5%, for example, 2 to 10% of a surfactant, and 5 to 95%, for example, 20 to 60% of a solid extender (for example, clay), and is formed by adding water to form a paste, followed by drying. Granulated water-dispersible granules and 0.05 to 90%, preferably 1 to 60% of one or more compounds of formula (I) and 0.01 to 10%, preferably 1 to 10% interface Activator and 9.99-99.
An emulsion containing 94%, preferably 39 to 99.99% of an organic solvent.

The herbicidal compositions according to the invention comprise one or more other pesticidally active compounds and, if desired, one or more compatible pesticidally acceptable bulking agents or carriers, surfactants and the aforementioned The conventional adjuvants comprise the compound of the formula (I) together with, preferably, a homogeneous dispersion of the compound of the formula (I) therein.

Examples of other pesticidally active compounds that can be mixed with or used in combination with the herbicidal composition of the present invention include herbicides, for example, arachlor [2] -Chloro-2,6'-diethyl-N- (methoxymethyl)
-Acetanilide], 1- (4,6-dimethoxypyrimidin-2-yl) -3-
Amidosulfuron (amidosu) which is mesyl (methyl) sulfamoylurea
ifuron), atrazine [2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine], bromoxynil [3,5-dibromo-4]
-Hydroxybenzonitrile], chlorotoluron [N '-(3-chloro-4-methylphenyl) -N, N-dimethylurea], (Z) -2-chloro-3- [2-chloro-5- (1, 3-dioxo-1,3,4,5,6,7-hexahydroisoindol-2-yl) -phenyl] -cinidone-ethyl ethyl acrylate, 3,6-dichloropyridine- Clopyralid, a 2-carboxylic acid, cyanazine [2-chloro-4-
(1-cyano-1-methylethylamino) -6-ethylamino-1,3,5-triazine], 2,4-D [2,4-dichlorophenoxyacetic acid], dicamba [3
6-dichloro-2-methoxybenzoic acid], dicloprop-P which is (R) -2- (2,4-dichlorophenoxy) propionic acid
, Difenzoquat [1,2-dimethyl-3,5-
Diphenyl-pyrazolium salt], 2 ′, 4′-difluoro-2- (α, α, α-
Diflufenican, which is a trifluoro-m-tolyloxy) nicotineanilide (
diflufenican), (R) -2- [4- (6-chloro-1,3-benzoxazol-2-yloxy) phenoxy] propionic acid, phenoxaprop-p-ethyl, furanpropmethyl (Flampropmethyl) [methyl N-2- (N-benzoyl-3-chloro-4-fluoroanilino) -propionate], 2 ', 6'-difluoro-5-methyl [1,2,4] triazolo [1 , 5-a] pyrimidine-2-sulfonanilide, flumethoslam, fluometuron [N '-(3-trifluoro-methylphenyl) -N, N-dimethylurea],
Flupyrsulfuron, 2- [2- (4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl)]-6-trifluoromethylpyridine-3-carboxylic acid, (RS) -5-methyl Amino-2
-Phenyl-4- (α, α, α-trifluoro-m-tolyl) furan-3 (2H
) -One, flurtamone, 2- (4-methyl-6)
-Methoxy-1,3,5-triazin-2-ylcarbamoylsulfamoyl)
Iodosulfuron, which is -4-iodobenzoic acid;
4-hydroxy-3,5-diiodobenzonitrile ioxinyl, 2-chloro-5- [4-chloro-5- (1,1-difluoromethoxy) -1-methyl-
1H-pyrazol-3-yl] -4-isopropylbenzoate isopropyl, 3- (4
-Isopropylphenyl) -1,1-dimethylurea, isoproturon, (R
) -2- [4- (6-Chlorobenzoxazol-2-yloxy) phenoxy] propionic acid, 5- [4-bromo-1-methyl-5- (trifluoromethyl)
-1H-pyrazol-3-yl] -2-chloro-4-fluorobenzoic acid
V-485, (R) -2- (4-chloro-o-tolyloxy) propionic acid, mecoprop-P, 2 ', 6'-dichloro-5,7
-Methmethoxy, dimethoxy-3'-methyl [1,2,4] triazolo [1,5-a] pyrimidine-2-sulfonanilide, 2- (4
-Methoxy-6-methyl-1,3,5-triazin-2-ylcarbamoylsulfamoyl) methyl benzoate, metsulfuron-methyl
ron-methyl), N- (1-ethylpropyl) -2,6-dinitro-3
, 4-xylysine pendimethalin, N-
(4-fluorophenyl) -6- (3-trifluoromethylphenoxy) -pyridine-2-carboxamide, picolinafen,
Insecticides such as synthetic pyrethroids such as permethrin and cypermethrin, and fungicides such as carbamates such as methyl N- (1-butyl-carbamoyl-benzimidazol-2-yl) carbamate and triazoles such as 1 -(4-chlorophenoxy) -3,3-dimethyl-1- (1,
2,4-triazol-1-yl) -butan-2-one.

The agrochemically active compounds and other biologically active substances, such as the acids or bases mentioned above, which can be incorporated in or used in combination with the herbicidal compositions according to the invention, if desired, can be in the form of conventional derivatives. For example, they can be used in the form of alkali metal salts, amine salts, and esters.

The following examples illustrate the herbicidal compositions according to the present invention. Trademarks that appear in the examples are Synperonic, Solvesso, Alylan, Arko
pon, Sopropon, Tixosil, Soprophor, Attag
el, Rhodorsil. The active ingredient in the following examples is represented by the general formula (
It means the compound of I).

[0194]Example C1  Active ingredient 20% w / v N-methylpyrrolidinone (NMP) 25% w / v Calcium dodecylbenzenesulfonate (CaDDBS) 4% w / v (Arylan CA) Nonylphenol / ethylene oxide / propylene oxide condensate (NPEOPO) (Syperonic NPE) 1800) 6% w / v
NMP, Active Ingredient (Compound 1), CaDDBS, NPEOPO, and
And aromatic solvent (Aromatic solvent)
Prepare a clear solution and then adjust the volume with an aromatic solvent
Thus, an emulsion is prepared.

[0195]Example C2  Active ingredient 50% w / w Sodium dodecylbenzenesulfonate (Arylan SX85) 3% w / w Sodium methyl oleoyl taurate (Arkopon T) 5% w / w Sodium polycarboxylate (Sopropon T36) 1% w / w Fine particles The above components were mixed together using 3% w / w of silicon dioxide (Tixosil 38) w / w China Clay 38% w / w, and the resulting mixture was pulverized with an air jet mill.
To produce a wettable powder.

[0196]Example C3  Active ingredient 50% w / v Cryoprotectant (propylene glycol) 5% w / v Ethoxylated tristyryl phenol phosphate (Soprophor FL) 0.5% w / v Nonylphenol 9 mol ethoxylate (Ethylan BCP) 0.5% w / V sodium polycarboxylate (Sopropon T36) 0.2% w / v Attaclay (Attagel) 1.5% w / v defoamer (Rhodorsil AF426R) 0.003% w / v water up to 100 Suspending agent by mixing the above components with each other and grinding with a bead mill
Is prepared.

[0197]Example C4  Active ingredient 50% w / w Sodium dodecylbenzenesulfonate (Arylan SX85) 3% w / w Sodium methyl oleoyl taurate (Arkopon T) 5% w / w Sodium polycarboxylate (Sopropon T36) 1% w / w Binder (Sodium lignosulfonate) 8% w / w China clay 30% w / w Fine particle silicon dioxide (Tixosil 38) 3% w / w The above components are mixed with each other, and the mixture is pulverized by an air jet mill. ,The water
In addition, granulation and drying in suitable granulation equipment (eg fluid bed dryer)
To prepare a water-dispersible suspension. Optionally, the active ingredient can be ground alone
Alternatively, it can be ground by mixing with all or a part of other components.

The following non-limiting examples illustrate the invention.

[0199]Experimental Example 1  Sow various broadleaf and grass weed species and mix in acetone and water.
The dissolved herbicide was sprayed on the soil surface at a rate of 62 g / ha. The weeds areAma
lanthus retroflexus,Abutilon theophr
asti,Gallium aparine,Setaria viridis, Alopecurus myosuroides ,Avena fatua,
AndEchinochloa crus-galliIt is.

The rate of decrease in plant growth two weeks after the treatment was evaluated in comparison with an untreated control group.

Compounds 1, 2, 5, 42, 43, 45, 62, 74, 85, 131, 132,
For 133, 134, 135, 136, 137, 140, 149, 159, the growth of one more weed species was reduced by 100%.

Compounds 3, 6, 7, 8, 18, 19, 20, 35, 36, 38, 39, 40,
44, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59,
60, 61, 63, 64, 66, 68, 75, 76, 78, 79, 80, 81,
82, 83, 84, 87, 88, 89, 90, 92, 93, 94, 97, 99,
100, 101, 109, 110, 112, 113, 114, 115, 116,
118, 119, 120, 122, 123, 125, 126, 128, 129,
For 130, 138, 150, 152, 156, 160, 163, 166, the growth of one more weed species was reduced by at least 80%.

Compounds 10, 12, 15, 16, 26, 28, 31, 65, 67, 69, 71
, 73, 77, 86, 91, 95, 96, 103, 111, 121, 124, 1
27, 145, 146, 148, 154, 155, 157, 161, 162, 1
For 64 and 167, the growth of one more weed species was reduced by at least 70%.

[0204]Experimental Example 2  Sow of the same kind of weed species as those listed in Example 1 and grown to 1-3 leaf stage
I let you. A herbicide dissolved in a mixture of acetone and water is dispersed at a rate of 62 g / ha after budding.
Clothed.

The rate of decrease in plant growth two weeks after the treatment was evaluated in comparison with an untreated control group.

Compounds 2, 49, 50, 51, 72, 78, 81, 82, 83, 84, 85,
88, 90, 92, 93, 94, 95, 99, 101, 118, 119, 120
, 131, 132, 133, 134, 135, 136, 137, 140, 149
, 152, 153, 156, 167, the growth of one more weed species was 10
It decreased by 0%.

Compounds 3, 4, 5, 10, 16, 18, 19, 20, 35, 43, 45, 46
, 47, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62
, 63, 64, 65, 66, 67, 68, 69, 70, 71, 73, 74, 75
, 76, 77, 79, 80, 86, 87, 89, 91, 96, 97, 98, 10
0, 102, 103, 109, 110, 111, 112, 113, 114, 11
5, 116, 117, 121, 122, 123, 124, 125, 126, 12
8, 129, 130, 138, 141, 150, 154, 155, 157, 15
8, 159, 160, 161, 162, 163 reduced the growth of one more weed species by at least 80%.

Compounds 17, 21, 26, 42, 48, 139, 142, 143, 144, 1
For 45, 146 and 148, the growth of one more weed species is at least 70%
Dropped.

In another embodiment of the present invention, a method comprising applying a detoxifying effective amount of an antidote (safener) effective for a compound of the present invention to a crop site or crop seeds, comprising: It is an object of the present invention to provide a method for reducing phytotoxicity (phytotoxicity) on crops caused by the compound of I).

Crops that can be protected by the method of the present invention include cereals, corn,
Rice, wheat, soybean, sorghum, and cotton. The method of the present invention comprises:
It is preferably carried out when the crop to be protected is corn or cereals, especially wheat.

The amount of antidote used in the compositions of the present invention may vary depending on the particular antidote used, the crop to be protected, the application rate of the herbicide used, and the overall soil and climatic conditions. Will vary depending on the factors. Also, the selection of a particular antidote to be used in the method of the present invention, the method of dispersing the antidote, and the determination of non-phytotoxic but detoxifying activity have been commonly performed in the art. It can be easily implemented according to the method.

“Non-phytotoxic” means an amount of an antidote with little or no harm to the desired crop species. "Detoxification effectiveness" means an antidote used in an antidote effective amount to reduce the degree of harm to the desired crop species by the herbicide.

Preferably, the weight ratio of herbicide (a) to antidote (b) is from about 16: 1 to about 0.25:
1, preferably from about 8: 1 to about 0.5: 1, more preferably from 2: 1 to 1: 1.
It is about 1: 1.

Examples of suitable antidote for use in the present invention include the following (where alkyl, alkenyl, alkynyl, and alkoxy groups, and portions thereof are as defined above). Cycloalkyl and phenyl are optionally substituted as defined above; halogen is as defined above; cycloalkenyl is a group having from 3 to 6 carbon atoms in the ring. And optionally substituted with lower alkyl, lower alkenyl, lower alkynyl, lower haloalkyl, and halogen; bicycloalkyl is a compound in which one of the rings contains 5-8 carbon atoms and the other ring has 3-6 carbon atoms. Means a saturated fused bicycloalkane containing 5 carbon atoms and optionally substituted with lower alkyl or halogen): (i) a compound of formula (VIII): R ^{7 0-} CO-NR ⁷² R ⁷¹ (VIII) wherein R ⁷⁰ is haloalkyl, haloalkenyl, alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, halogen, hydrogen, carboalkoxy,
N-N-alkynylcarbamylalkoxyalkyl, N-alkenylcarbamylalkoxyalkyl, N-alkyl-N-alkynylcarbamylalkoxyalkyl, alkynyloxy, haloalkoxy, thiocyanatoalkyl, alkenylaminoalkyl, alkylcarboalkyl, cyanoalkyl , Cyanatoalkyl, alkenylaminosulfonalkyl, alkylthioalkyl, haloalkylcarbonyloxyalkyl, alkoxycarboalkyl, haloalkenylcarbonyloxyalkyl, hydroxyhaloalkyloxyalkyl, hydroxyalkylcarboalkyloxyalkyl, hydroxyalkyl, alkoxysulfonoalkyl, furyl, Thienyl, alkyldithiorenyl, thienalkyl, phenyl, substituted phenyl (where the substituent , Halogen, alkyl, haloalkyl, alkoxy, carbamyl, nitro, carboxy and salts thereof, and haloalkylcarbamyl), phenylalkyl, phenylhaloalkyl, phenylalkenyl, substituted phenylalkenyl, wherein the substituent is halogen , Alkyl,
Alkoxy, and halophenoxy), phenylalkoxy, phenylalkylcarboxyalkyl, phenylcycloalkyl, halophenylalkenoxy, halothiophenylalkyl, halophenoxyalkyl,
Can be selected from the group consisting of bicycloalkyl, alkenylcarbamylpyridinyl, alkynylcarbamylpyridinyl, dialkenylcarbamylbicycloalkenyl, and alkynylcarbamylbicycloalkenyl, wherein R ⁷¹ and R ⁷² are the same or different. Well, alkenyl, haloalkenyl,
Hydrogen, alkyl, haloalkyl, alkynyl, cyanoalkyl, hydroxyalkyl, hydroxyhaloalkyl, haloalkylcarboxyalkyl, alkylcarboxyalkyl, alkoxycarboxyalkyl, thioalkylcarboxyalkyl, alkoxycarboalkyl, alkylcarbamyloxyalkyl, amino, formyl, haloalkyl- N-alkylamide, haloalkylamide, haloalkylamidoalkyl, haloalkyl-N-alkylamidoalkyl, haloalkylamidoalkenyl, alkylimino, cycloalkyl, alkylcycloalkyl, alkoxyalkyl, alkylsulfonyloxyalkyl, mercaptoalkyl, alkylaminoalkyl, alkoxy Carboalkenyl, haloalkylcarbonyl, al Carbonyl, alkenylcarbamyloxyalkyl, cycloalkylcarbamyloxyalkyl, alkoxycarbonyl, haloalkoxycarbonyl, halophenylcarbamyloxyalkyl, cycloalkenyl, phenyl, substituted phenyl (where the substituent is alkyl, halogen, haloalkyl , Alkoxy, haloalkylamide, phthalimide, hydroxyl, alkylcarbamyloxy, alkenylcarbamyloxy, alkylamide, haloalkylamide, and alkylcarboalkenyl), phenylsulfonyl, substituted phenylalkyl (wherein the substituent Can be selected from halogen or alkyl), dioxyalkylene, halophenoxyalkylamido-alkyl, alkylthiodiazolyl Piperidyl, piperidyl alkyl, di oxolanyl alkyl, thiazolyl, alkyl thiazolyl, benzothiazolyl,
Halobenzothiazolyl, furyl, alkyl-substituted furyl, furylalkyl, pyridyl, alkylpyridyl, alkoxyazolyl, tetrahydrofurylalkyl, 3
-Cyano-thienyl, alkyl-substituted thienyl, 4,5-polyalkylenethienyl, α-haloalkylacetamidophenylphenylalkyl, α-haloalkylacetamidonitrophenylalkyl, α-haloalkylacetamidohalophenylalkyl, and cyanoalkenyl Or a combination of R ⁷¹ and R ⁷² is piperidinyl, alkylpiperidinyl, pyridyl, dihydropyridinyl or tetrahydropyridinyl, alkyltetrahydropyridyl, morpholyl, azabicyclononyl, diazacycloalkanyl, benzo Alkylpyrrolidinyl, oxazolidinyl, perhydrooxazolidinyl,
Alkyl oxazolidinylcarbonyl, furyl oxazolidinylcarbonyl, thienyl oxazolidinylcarbonyl, pyridyl oxazolidinylcarbonyl, pyrimidinyl oxazolidinylcarbonyl, benzo oxazolidinylcarbonyl, C _3.7 spiro cycloalkyl - oxazolidinyl, alkylamino alkenyl, Alkylideneimino, pyrrolidinyl, piperidonyl, perhydroazepinyl, perhydroazosinyl, pyrazolyl, tetrahydroquinolyl, tetrahydroisoquinolyl, perhydroquinolyl, perhydroisoquinolyl, indolyl, or dihydroindolyl, or perhydroin can form a structure consisting of a drill, a portion combining R ⁷¹ and R ⁷² may be substituted by independent R ⁷¹ groups and R ⁷² groups listed above); or (ii) the following compounds One of the : Alpha - [(cyanomethoxy) imino] benzene acetonitrile, α - [(1,3
-Dioxolan-2-ylmethoxy) imino] -benzeneacetonitrile, O-
[3-dioxolan-2-ylmethyl] -2,2,2-trifluoromethyl-4
'-Chloroacetophenone oxime, N- [4- (dichloromethylene) -1,3
-Diotran-2-ylidene] -α methyl hydrochloride benzene methamine, diphenylmethoxyacetic acid methyl ester, 1,8-naphthalic anhydride, 4,6-dichloro-2-phenylpyrimidine, 2-chloro-N- [ 1- (2,4,6-trimethylphenyl) ethenyl] acetamide, ethylene glycol acetal of 1,1-dichloroacetone, 4-dichloroacetyl-3,4-dihydro-3-methyl-
Benoxacor, which is 2H-1,4-benzoxazine,
Dichloromide (dic, which is N, N-diallyl-2,2-dichloroacetamide)
lormid), fenclorim, which is 4,6-dichloro-2-phenylpyrimidine, (RS) -3-dichloroacetyl-5- (2-
Furilazole which is furanyl) -2,2-dimethyloxazolidine
azole), cloquintocet (5-chloroquinolin-8-yloxy acid) or salts or esters thereof, such as cloquintocet-mexyl ((5-chloroquinolin-8-yloxy) acetic acid 1) -Mexylhexyl), fenchlorazole (f
enchlorazole) (1- (2,4-dichlorophenyl) -5-trichloromethyl) -1H-1,2,4-triazole-3-carboxylic acid), or a salt or ester thereof, such as fenchlorazole-ethyl
zole-ethyl) (ethyl 1- (2,4-dichlorophenyl) -5-trichloromethyl) -1H-1,2,4-triazole-3-carboxylate), mefenpyr-ethyl (1- ( 2,4-dichlorophenyl) -5-methyl-2-pyrazolin-3,5-dicarboxylic acid diethyl), 5
R29148 which is 2,5-diphenylisoxazolinone-3-carboxylic acid and 2,2-dichloro-1- (2,2,5-trimethyloxazolidine-3-yl) -ethanone.

Particularly preferred antidotes for use in the present invention are cloquintocet, cloquintocet-mexyl, fenchlorazole, fenchlorazole-ethyl, benoxacor, and R29148.

The present invention is illustrated by the following non-limiting examples.

[0219]Experimental example 3  Compounds of formula (I) (hereinafter "herbicides") and flurilazole (flurilil)
azole), benoxacor, dichloromid, cloquinto set, fenchlora
Sol, naphthalic anhydride, and R29148, alone and in tank mixtures.
An experiment was conducted to examine the damage to corn and wheat after spraying after emergence.

The herbicides furilazole, benoxacol, dichloromid, cloquintocet, fenchlorazole, naphthalic anhydride, and R29148 were used as technical materials prepared in acetone. A mixture of herbicide and safener was applied after emergence. Two weeks after the treatment, the rate of decrease in plant growth was evaluated in comparison with an untreated control group (only herbicide sprayed).

The safener reduced the degree of harm caused by the herbicide and provided a detoxifying effect on corn and wheat.

[0220]Experimental example 4  Gallium aparineAnd wheat (Triticum aestivu
m), Where the natural population is formed, is a representative compound of formula (I)
Compounds 2 and 82 and Cloquintocet-Mexil were prepared in acetone
Used as technical material.

The respective components and mixtures of Compound 2, Compound 82 and Cloquintocet-mexyl were applied later after emergence of the weeds and crops.

The rate of reduction in plant growth was evaluated 12 days and 25 days after treatment (DAT) in comparison with the untreated control group.

The results obtained are summarized in the following table.

[0224]

[Table 18]

[0225]

[Table 19]

[0226]

[Table 20]

[0227]

[Table 21]

[0228]Experimental example 5  Gallium aparineAnd wheat (Triticum aestivu
m) Are representative of compounds of formula (I) where the sting population is formed
Compounds 2 and 82 and Cloquintocet-Mexil were prepared in acetone.
Used as technical material manufactured.

The respective components and mixtures of Compound 2, Compound 82 and Cloquintocet-mexyl were applied later after emergence of the weeds and crops.

The rate of reduction in plant growth was evaluated 20 days and 33 days after treatment (DAT) in comparison with the untreated control group.

The results obtained are summarized in the following table.

[0232]

[Table 22]

[0233]

[Table 23]

[0234]

[Table 24]

[0235]

[Table 25]

According to a further feature of the present invention, there are provided (a) an aryl vinyl ether derivative as defined by the general formula (I) or an agriculturally acceptable salt or metal complex thereof, and (b) an antidote as defined above. And providing the product as a combined preparation for simultaneous, separate or sequential use, such as for controlling weed growth in places such as cultivated lands.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 217/58 C07C 217/58 4C069 235/64 235/64 4C204 247/10 247/10 4H006 255/37 255 / 37 4H011 259/06 259/06 271/16 271/16 323/54 323/54 323/58 323/58 C07D 207/452 C07D 207/452 209/48 211/78 211/78 213/54 213/54 213/70 213/70 213/77 213/77 213/80 213/80 249/18 503 249/18 503 295/22 Z 295/22 307/12 307/12 307/88 307/88 307/89 Z 307 / 89 317/22 317/22 317/54 317/54 333/40 333/40 339/06 339/06 209/48 Z (31) Priority claim number 9826903.8 (32) Priority date December 1998 7th (1998.12.7) (33) Priority country United Kingdom (GB) (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, B, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE , AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW , MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZA, ZW (72) Inventor Wight, Catherine Jacqueline UK, Esetsux C.M.5 OH. , Huayfield Road, Research Station, Rhone-Poulenc-Agrica Lucia Limited (no address) (72) Inventor Gingier, Michael United Kingdom Huayfield Road, Research Station, Rhone-Poulenc-Agrica Lucia Limited (no address) (72) Inventor Petitet, Simon Neil United Kingdom , Faifield Road, Research Station (72) Inventor Lahuy, Jill United Kingdom, Esetsux C.M.5 OH Daville, Ongar, Huayfield Road, Research Station, Rh ヌ ne-Poulenc Agricca Lucia Limited (No address) F-term (reference) 4C022 BA05 EA02 4C023 HA02 NA01 4C037 CA08 RA09 RA11 4C054 AA03 BB01 CC01 DD32 DD33 EE04 EE12 EE25 FF01 4C055 AA01 BA02 BA02 BA01 BA02 BA01 CB AD08 4C204 BB02 CB04 DB30 EB03 FB01 FB02 GB14 GB25 4H006 AA01 AA03 AB04 BJ50 BM30 BN30 BP30 TA04 TB04 TC32 4H011 AB01 AB02 BA01 BA03 BB06 BB09 BC03 BC06 BC07 BC08 BC17 BC18 DA15 DA16 DD04

Claims (21)

[Claims] 1. An aryl vinyl ether derivative of the general formula (I):Wherein p is 0 or 1, X¹Is O, NH, or S; X²Is O, S, NR¹⁸Or a single bond; X³Is N or CR¹⁹R¹⁷And R¹⁸Are independently a hydrogen atom or an optionally substituted group R²⁰,
R²¹, R²²Or R²³Represents R²⁰Represents a lower alkyl group; R²¹Represents a lower alkenyl group; R²²Represents a lower alkynyl group; R²³Is-(CH₂)_m-Represents a phenyl group; m represents 0 or 1;¹⁶Is R²⁴, OR²⁵, SR²⁵, NR²⁵R²⁶Or
Alkyl substituted with alkoxycarbonyl; R²⁴, R²⁵, And R²⁶Is independently R¹⁸Has one of the meanings given to
R;¹⁹Is R¹⁶R has one of the meanings given above; R¹⁰Is -CH₂NO₂, -CHR²⁷R²⁸, -CR²⁷R²⁸R²⁸¹, -CR³⁰ R²⁹R²⁹¹, -CO-NR³⁰R³¹, -CH₂NR³⁰R³¹, -CH =
CR³¹R³², -CH₂N (R³⁰) S (O)_qR³³, -C (O) SR³² , -CH₂C (O) SR³²,-(CH₂)_zCO₂R³², -CO₂R³²,
-CH = CHC (O) OR³², -C (R³²) = N-NR³⁰R³¹, -C (
R³²) = N—NH—C (O) lower alkyl, —COR³², -C (O) OC (
O) R³², -C (= N-OH) R³², -C @ CCOOR³², -CH₂SC
N, -CH₂NCO, -CH₂NCS, -CH₂N₃, -CH₂CN, -CH₂ OSCN, -CH₂OCN, -CH₂N (R³⁰) CO₂R³³, -CH₂OS
O₂R³³, -CH₂SO₂OR³³, -CH₂OCO₂R³³, -CH = CH
NR³³R³⁴, -C (O) ONR³³R³⁴, -C (= NR³⁵) R³², −
CH₂P (O) R³⁵R³⁶, -CH₂OP (O) R³⁵R³⁶, -CH₂OC
(O) NR³⁰R³⁶, -CH₂OCH₂C (O) (optionally substituted phenyl
), -CO₂N = C (optionally substituted phenyl)₂, N-succinimide meth
, N-phthalimidomethyl, tetrazolyl group (particularly 1-tetrazolyl), -C
ONNHHR³⁰, -CO₂CH₂CO (optionally substituted phenyl, or
Saturated or unsaturated containing 1 to 3 heteroatoms selected from O, N, and S
A 5- to 7-membered heterocyclic ring), -CO₂CH₂(1 to 3 selected from O, N, and S
Saturated or unsaturated 5- to 7-membered heterocycle containing two heteroatoms), CO₂R^32a,
COCH₂COR³³, COCHN₂, CONH (a lower alkyl substituted with a hydroxyl group)
Kill), -CH (OH) (lower alkyl), C (R³²) = N-NH-C (S)
NR^a, C (R³²) = N-NH (optionally substituted, selected from O, N, and S
Unsaturated 5 to 7 membered heterocyclic ring containing 1 to 3 heteroatoms), C (R³²) =
N-NR^30aR^31a, C (R³²) = N-NHSO₂R³³, And C (O
R) represents a group selected from: F, z represents 1, 2, 3, or 4; q represents 0 or 2, R^aRepresents H or lower alkyl; R^32aIs an N-linked imidazo optionally substituted and optionally fused to a benzene ring
A ring or a triazole ring; R^30aAnd R^31aAnd the N atom to which they are attached
O, S or NR^aA 5- or 6-membered saturated heterocycle optionally containing a group in the ring
Forming; R²⁷, R²⁸, And R²⁸¹Represents a same or different halogen atom; R²⁹And R²⁹¹Is OR³⁷Or SR³⁷Or R²⁹And R²⁹¹Form a divalent group and combine with
5- or 6-membered cyclic acetal or thioacetal combined with carbon atoms
Forming a ring, wherein said ring structure is optionally substituted with one or more lower alkyl groups;³⁰, R³¹, And R³²Is independently hydrogen, lower alkyl, lower haloal
Kill, lower alkoxyalkyl, lower alkenyl, lower haloalkenyl, lower
Ruquinyl, lower haloalkynyl, optionally substituted cycloalkyl, optionally substituted
-(CH₂)_mRepresents phenyl; R³³And R³⁴Is R other than a hydrogen atom³²R;³⁵And R³⁶Represents a hydrogen atom or represents an alkyl, alkoxy, or
Or a group which may be any of optionally substituted phenyl; R³⁷Is lower alkyl, lower haloalkyl, lower alkenyl, or lower ha.
R represents alkenyl; R¹¹And R¹³Each independently represents hydrogen or alkyl, or
Is R¹¹And R¹³Form a single bond together with the carbon bond to which they are attached
May form a double bond, or R¹¹And R¹³Is a divalent group containing 1 to 6 atoms in the main chain.
The main chain can be one to three nitrogen atoms, one oxygen atom, or one sulfur atom.
Optionally containing an atom; the sum of the divalent group and the two carbon atoms to which it is attached
Form a saturated or unsaturated carbocyclic or heterocyclic or bicyclic ring,
Has 1 to 4 R^FifteenEach ring is optionally substituted by groups, and each ring is at most an 8-membered ring;
Preferably a maximum of 6 membered rings, where R^FifteenIs a halogen atom, hydroxyl group, cyano, lower alkoxycarbon
, Lower alkyl, lower alkenyl, lower alkynyl, optionally substituted cyclo
Alkyl, lower alkoxy, lower alkylthio, lower alkylsulfinyl, lower
Lower alkylsulfonyl, lower haloalkoxycarbonyl, lower haloalkyl, low
Lower haloalkenyl, lower haloalkynyl, halocycloalkyl, lower haloalk
Xy, lower haloalkylthio, lower haloalkylsulfinyl, lower haloalkyl
Rusulfonyl, nitro, amino, lower alkylamino, lower dialkylamino,
Optionally substituted phenoxy, lower alkylcarbonylamino, carbamoyl,
Lower alkylcarbamoyl, lower dialkylcarbamoyl, -CH₂SCN, S
F₅, -CR³⁰= N-R³¹, -CR³⁰= NOR³¹, -CR³⁰= NNR ³⁰ R³¹, -CR³⁰R²⁹R²⁹¹, Alkoxyalkyl, CR^bR^cR^a , COR^a, Optionally substituted phenyl or naphthyl, or alkoxy
Carbonyl or CO₂Alkenyloxy substituted with H;^bAnd R^cAnd the C atom to which these are bonded are a 5- or 6-membered ring
Forming an acetal group; or R¹⁰R¹¹R¹²CC (R¹³) (R¹⁴)-Is a group (A), (B
), (C), (D), or (E):Wherein R is^d, R^e, R^f, R^g, And R^hIs H, lower alkyl, halo
And n represents a value of 0, 1, 2, or 3; R¹⁵¹Is R^FifteenOr a hydrogen atom; R¹²And R¹⁴Each independently represents hydrogen or alkyl, or
May form a double bond together with a single bond, in which case R¹¹And R¹³ Are combined to form one divalent group; preferably, the following condition is satisfied; i) R¹⁰R¹¹R¹²CC (R¹³) (R¹⁴)-Is R^FifteenReplace with any
R represents a substituted phenyl ring;¹⁰Is -CO₂R³², CONR³⁰R³¹, CH
R²⁷R²⁸Or CR²⁷R²⁸R²⁸¹And R in the formula³²Is alkyl
Or haloalkyl; R³⁰And R³¹Represents H or alkyl; ²⁷ , R²⁸, And R²⁸¹Is as defined above; p is 0; X₁ Is O; X₂Is O; X₃Is CH; R¹⁶Is OR²⁵If it is
R^FifteenIs not a monohalomethyl group; ii) R¹⁰R¹¹R¹²CC (R¹³) (R¹⁴)-Is EtO₂C-CH
= CH-; p is 1; X₁Is S; X₂Is a bond; R¹⁷ Represents phenyl; X₃Is CH; R¹⁶Is NH₂And NMe₂not
Iii) R¹¹, R¹², R¹³, R¹⁴Each represents H; p is 1
R; X₁Is S and X₂Is O; R¹⁷Represents Et; X₃Is N;
R¹⁶Represents -NH (4-nitrophenyl); R¹⁰Is CO₂H and CON
Not HPh; iv) R¹¹, R¹², R¹³, R¹⁴Each represents H; p is 0 and
X₁Is S and X₂Is O; R¹⁷Represents Et; X₃Is N; R ¹⁶ Represents -NH (4-nitrophenyl); R¹⁰Is CO₂H and CONH ₂ Not; v) p represents 0; X₁Is O; X₂Is a bond; R¹⁷Represents H;
X₃Is CH; R¹⁶Is NMe₂R;¹⁰R¹¹R¹²CC (R^{1 3} ) (R¹⁴)-Is 5-methyl-2-R¹⁰Represents a -substituted-thien-3-yl group
Case; R¹⁰Is CO₂H and CO₂Not Me; vi) R¹¹, R¹², R¹³, R¹⁴Each represents H; p is 0 and
X₁Is S and X₂Is O; R¹⁷Represents H; X₃Is N; R^{1 6} Is -NH (4-nitrophenyl); R¹⁰Is CO₂Not H; vii) R¹⁰Is CO₂Represents Et; R¹¹, R¹², R¹³, And R¹⁴ Each represents H; p is 0;₁Is S; X₂Is NH and R^{1 7} Represents phenyl; X₃Is CMe; R¹⁶Is NH₂And in NHMe
None; viii) p is 0; X₁Is O; X₂Is O; R¹⁷Is Me
Represents; X₃Is CH; R¹⁶Represents OMe; R¹⁰R¹¹R¹²CC (
R¹³) (R¹⁴)-Is 1,3-dimethyl-4-R¹⁰-Substituted-pyrazole-5
-Yl group; R¹⁰Is not 4-chlorobenzoyl] and their agriculturally acceptable salts and metal complexes. 2. p is 0 or 1, X¹Is O, NH, or S; X²Is O, S, NR¹⁸Or a single bond; X³Is N or CR¹⁹R¹⁷And R¹⁸Are independently a hydrogen atom or an optionally substituted group R²⁰,
R²¹, R²²Or R²³Where R²⁰Represents a lower alkyl group; R²¹Represents a lower alkenyl group; R²²Represents a lower alkynyl group; R²³Is-(CH₂)_m-Represents a phenyl group; m represents 0 or 1;¹⁶Is R²⁴Or OR²⁵Or SR²⁵Or NR²⁵R²⁶Is
R²⁴, R²⁵, And R²⁶Is independently R¹⁸Has one of the meanings given to
R;¹⁹Is R¹⁶R has one of the meanings given to R¹⁰Is -CH₂NO₂, -CHR²⁷R²⁸, -CR²⁷R²⁸R²⁸¹, -CR³⁰ R²⁹R²⁹¹, -CO-NR³⁰R³¹, -CH₂NR³⁰R³¹, -CH =
CR³¹R³², -CH₂N (R³⁰) S (O)_qR³³, -C (O) SR³² , -CH₂C (O) SR³², -CH₂CO₂R³², -CO₂R³², -CH
= CHC (O) OR³², -C (R³²) = N-NR³⁰R³¹, -C (R³² ) = N—NH—C (O) lower alkyl, —COR³², -C (O) OC (O) R ³² , -C (= N-OH) R³², -C @ CCOOR³², -CH₂SCN,-
CH₂NCO, -CH₂NCS, -CH₂N₃, -CH₂CN, -CH₂OSC
N, -CH₂OCN, -CH₂N (R³⁰) CO₂R³³, -CH₂OSO₂R ³³ , -CH₂SO₂OR³³, -CH₂OCO₂R³³, -CH = CHNR^{3 3} R³⁴, -C (O) ONR³³R³⁴, -C (= NR³⁵) R³², -CH₂ P (O) R³⁵R³⁶, -CH₂OP (O) R³⁵R³⁶, -CH₂OC (O)
NR³⁰R³⁶, -CH₂OCH₂C (O) (optionally substituted phenyl),-
CO₂N = C (optionally substituted phenyl)₂, N-succinimidomethyl, N
R represents a group selected from -phthalimidomethyl or a tetrazolyl group (particularly 1-tetrazolyl); q represents 0 or 2; R²⁷, R²⁸, And R²⁸¹Represents a same or different halogen atom;²⁹And R²⁹¹Is OR³⁷Or SR³⁷Or R²⁹And R²⁹¹Form a divalent group and combine with
5- or 6-membered cyclic acetal or thioacetal combined with carbon atoms
Forming a ring, wherein said ring structure is optionally substituted with one or more lower alkyl groups;³⁰, R³¹, And R³²Is independently hydrogen, lower alkyl, lower haloal
Kill, lower alkoxyalkyl, lower alkenyl, lower haloalkenyl, lower
Ruquinyl, lower haloalkynyl, optionally substituted cycloalkyl, optionally substituted
-(CH₂)_mRepresents phenyl; R³³And R³⁴Is R other than a hydrogen atom³²R;³⁵And R³⁶Represents a hydrogen atom or is an alkyl, alkoxy, or
Or a group which may be any of optionally substituted phenyl; R³⁷Is lower alkyl, lower haloalkyl, lower alkenyl, or lower ha.
R represents alkenyl; R¹¹And R¹³Each independently represents hydrogen or alkyl, or
Is R¹¹And R¹³Together form a single bond, together with the carbon atom to which they are attached
May form a double bond, or R¹¹And R¹³Represents one divalent group containing 1 to 6 atoms in the main chain.
The main chain can be one to three nitrogen atoms, one oxygen atom, or one sulfur atom.
Optionally containing an atom; the sum of the divalent group and the two carbon atoms to which it is attached
Form a saturated or unsaturated carbocyclic or heterocyclic or bicyclic ring,
Ring is R^FifteenOptionally substituted by groups, each ring being a maximum of 8 membered rings, preferably
A maximum of 6 membered rings, where R^FifteenIs a halogen atom, hydroxyl group, cyano, lower alkoxy carbonyl
, Lower alkyl, lower alkenyl, lower alkynyl, optionally substituted cyclo
Alkyl, lower alkoxy, lower alkylthio, lower alkylsulfonyl, lower
Alkylsulfonyl, lower haloalkoxycarbonyl, lower haloalkyl, lower
Haloalkenyl, lower haloalkynyl, halocycloalkyl, lower haloalkoxy
, Lower haloalkylthio, lower haloalkylsulfinyl, lower haloalkyl
Sulfonyl, nitro, amino, lower alkylamino, lower dialkylamino, any
Optionally substituted phenoxy, lower alkylcarbonylamino, carbamoyl, low
Lower alkylcarbamoyl, lower dialkylcarbamoyl, SF₅, -CR³⁰=
NR³¹, -CR³⁰= NOR³¹, -CR³⁰= NNR³⁰R³¹Or
-CR³⁰R²⁹R²⁹¹, R¹⁵¹Is R^FifteenOr a hydrogen atom; R¹²And R¹⁴Each independently represents hydrogen or alkyl, or
May form a double bond together with a single bond, in which case R¹¹And R¹³ Together form one divalent group; provided that R¹⁰R¹¹R¹²CC (R¹³) (R¹⁴)-Is R^FifteenArbitrarily
Represents a substituted phenyl ring;¹⁰Is -CO₂R³², CONR³⁰R³¹, C
HR²⁷R²⁸Or CR²⁷R²⁸R²⁸¹And R in the formula³²Is archi
R or haloalkyl; R³⁰And R³¹Represents H or alkyl;
R²⁷, R²⁸, And R²⁸¹Is as defined above; p is 0; X ₁ Is O; X₂Is O; X₃Is CH; R¹⁶Is OR²⁵Place that is
If; R^FifteenIs not a monohalomethyl group, the aryl vinyl ether derivatives of formula (I) according to claim 1,
Agriculturally acceptable salts and metal complexes. 3. The compound according to claim 1, wherein R ¹¹ and R ¹³ form a phenyl ring substituted with a halogen atom. 4. The method according to claim 1, wherein X ₃ represents CR ¹⁹ , and R ¹⁹ is a hydrogen atom.
4. The compound according to any one of 2, 3, or 3. 5. The compound according to claim 1, wherein X ₂ represents an oxygen atom. 6. The compound according to claim 1, wherein X ₁ represents an oxygen atom. 7. The compound according to claim 1, wherein R ¹⁷ represents methyl. 8. The compound according to claim 1, wherein R ¹⁶ is methoxy. 9. R¹⁰Is -CHR²⁷R²⁸(Where R²⁷And R²⁸ Is bromine), -COR³²Or -CO₂R³²(Where R³²Is lower class
Alkyl or hydrogen), -CH₂OSO₂R³³(R³³Is substituted phenyl
Represents), -CH₂NO₂, -CH₂OCH₂C (O) Ph, -CH₂OTs,-
C (R³²) = N-NHSO₂R³³(Where R³²Is hydrogen and R³³Is low
), -C (R³²) = N-NH-C (S) NR^a(Where R^{3 2} Is hydrogen and R^aIs lower alkyl), -C (R³²) = N-NR³⁰ R³¹(Where R³²And R³⁰Is hydrogen and R³¹Is optionally substituted-
(CH₂)_m-Phenyl), -C (R³²) = N−N^30aR^31a(This
Where R³²Is hydrogen and R^30aAnd R^31aIs the N atom to which they are attached
Together, additional O and NR^aForm a 6-membered saturated heterocyclic ring containing a group in the ring
), -C (R³²) = N-NH (optionally substituted nitrogen-containing unsaturated 6-membered complex
Ring) (where R³²Is hydrogen), -C (O) F, -CO₂CH₂CO (optional
Phenyl), -CO₂R^32a(Where R^32aIs optionally replaced
, An N-linked triazole ring fused to a benzene ring), -CO-NR³⁰R ³¹ (Where R³⁰Is hydrogen and R³¹Is lower alkyl), -CONH
NHR³⁰(Where R³⁰Is optionally substituted-(CH₂)_m-Is phenyl
), -C (R³²) = N-NH-C (O) lower alkyl (where R³²Is hydrogen
A), -C (O) SR³²(Where R³²Is lower alkyl), -CH (
OH) lower alkyl, -COCHN₂, -CR³⁰R²⁹R²⁹¹(Where R^{3 0} Is hydrogen and R²⁹And R²⁹¹Together form a divalent group,
The divalent group and the carbon atom to which the divalent group is combined are optionally substituted on a 5-membered ring
To form a thioacetal ring), -C (= N-OH) R³²(Where R³²Is low
Or-(CH₂)_zCO₂R³²(Where R³²Is hydrogen
, Lower alkyl, lower alkenyl, lower alkynyl, lower haloalkyl, lower
Lucoxyalkyl, optionally substituted-(CH₂)_m-Represents phenyl)
Or; R¹⁰R¹¹R¹²CC (R¹³) (R¹⁴)-Is a group A (here
In R^dAnd R^eRepresents hydrogen or halogen); R^FifteenIs -COR^a, Halogen, lower alkyl, lower alkoxy, lower halo
Alkoxy, lower alkoxycarbonyl, CR^bR^cR^a(Where R^bAnd R^cBut
Forming a 5-membered cyclic acetal group;^aRepresents hydrogen).
Compound. 10. The compound according to claim 1, wherein R ¹⁰ represents —COR ³² or CO ₂ R ³² , and R ³² represents lower alkyl or hydrogen. 11. R¹¹And R¹³Is one or more of a halogen, an alkyl group,
Or forming a phenyl or naphthyl ring substituted with a haloalkyl group; X₃ Is CR¹⁹And R¹⁹Represents a hydrogen atom; X₁And X₂Are oxygen sources
Represents a child; R¹⁶And R¹⁷Each represents a methyl group; R¹⁰Is -CO₂R ³² The compound of claim 1, wherein 12. R¹¹And R¹³Is one or more of a halogen, an alkyl group,
Or forming a phenyl or naphthyl ring substituted with a haloalkyl group; X₃ Is CR¹⁹And R¹⁹Represents a hydrogen atom; X₁And X₂Are oxygen sources
Represents a child; R¹⁶And R¹⁷Each represents a methyl group; R¹⁰Is -CO₂R ³² And R³²2. The compound according to claim 1, wherein is a lower alkyl or hydrogen.
. 13. Aryl vinyl ether derivatives of the general formula (I) according to claim 1 together with agriculturally acceptable extenders or carriers and / or surfactants or their agriculturally acceptable. A herbicidal composition comprising a herbicidally effective amount of a salt or a metal complex as an active ingredient. 14. A method for controlling weeds at a certain place, comprising the aryl vinyl ether derivative of the general formula (I) according to claim 1 or an agriculturally acceptable salt or metal complex thereof. A method comprising applying a herbicidally effective amount to said location. 15. The method according to claim 14, wherein the location is an area used for growing crops or an area to be used, and the compound is applied at an application rate of 1 g to 1000 g per hectare. 16. A method for reducing the phytotoxicity to agricultural crops caused by the arylvinyl ether derivative of the general formula (I) or an agriculturally acceptable salt or metal complex thereof according to any one of claims 1 to 12. And applying a safener effective amount of a safener effective against the compound to the whole cultivated land or seeds of the crop. 17. Weed growth in a certain place (for example, cultivated land) comprising (a) the aryl vinyl ether derivative according to claim 1 or an agriculturally acceptable salt or metal complex thereof and (b) a safener. As a combined preparation for simultaneous, separate or sequential use for controlling corn. 18. A process for producing the compound of the general formula (I) according to claim 1.
A) R¹¹, R¹², R¹³, R¹⁴, R¹⁶, R¹⁷, P, X₁, X₂,
And X₃Is as defined in claim 1, and R¹⁰Is -CO₂R³³Represents
, R³³Is R other than a hydrogen atom³²Is represented by R¹⁰Is CO₂The corresponding H
A compound of formula (I) is converted to a compound of formula (II): R³³—OH (II) (wherein R³³Is as defined in claim 1).
B) various symbols are as defined in claim 1;¹⁰Is -CO₂H
When represented, R¹⁰Is -CO₂R³³Represents R³³Is the corresponding t-butyl
Subjecting the compound to acid hydrolysis; c) various symbols are as defined in claim 1;¹⁰Is -CONR^{3 0} R³¹Is represented by R¹⁰Is -CO₂H represents a corresponding compound of formula (I)
Conversion to an acyl halide, followed by a compound of formula (III): R³⁰R³¹NH (III) (wherein R³⁰And R³¹Is as defined in claim 1);
D) various symbols are as defined in claim 1;¹⁰Is -CH₂NO ₂ , -CH₂SCN, -CH₂CN or -CH₂CN₃If R^{1 0} = -CH₂-L (where L is a leaving group) or Y = -CH₂-L is
-CH₂-L¹(Where L¹Is a leaving group) and the corresponding formula (
A compound of I) is converted to a suitable nitro anion, thiocyano anion, cyano anion
Or each of the metal salts of the azide anion; e) the various symbols are as defined in claim 1;¹⁰Is -C (= NR ³⁵ ) R³²If R¹⁰Is -COR³²Of the corresponding formula (I)
Compounds of formula (IV): R³⁵NH₂ (IV) (R in the formula³⁵Is as defined in claim 1), f) the various symbols are as defined in claim 1, R¹⁰Is -CH = CH
C (O) OR³²If R¹⁰Of the corresponding formula (I) wherein is a halogen
Compounds of formula (V): CH₂= CHC (O) OR³² (V) (R in the formula³²Is as defined in claim 1), and g) the various symbols are as defined in claim 1;¹⁰Is -CHR²⁷ R²⁸Or -CR²⁷R²⁸R²⁸¹And R²⁷, R²⁸, And R^{28 1} Is as described in claim 1, R²⁷, R²⁸, And R²⁸¹Of 1
Halogenating the corresponding compound, one or more of which has been replaced by a hydrogen atom, h) when the various symbols are as defined in claim 1, formula (VI)(Where R¹⁰, R¹¹, R¹², R¹³, R¹⁴, P, and X₁Is claim 1
With a compound of formula (VII)(Where X₂, X₃, R¹⁶, And R¹⁷Is as defined in claim 1.
L²Is a leaving group); i) the various symbols are as defined in claim 1;¹⁶Is OR²⁵¹To
Represents, R²⁵¹Is R other than a hydrogen atom²⁵In the case where is represented by the formula (VIII):(Wherein the various symbols are as defined in claim 1).
J) the various symbols are as defined in claim 1;¹⁰Is -COCH₂ COR³³And R³³Is as defined in claim 1, R¹⁰ Is a group -COCH (CO₂tBu) COR³³Of the corresponding compound replaced by
Hydrolyzing; k) various symbols are as defined in claim 1;¹⁰Represents -COF
R¹⁰Is CO₂Fluorinating the corresponding compound representing H, 1) various symbols are as defined in claim 1;¹⁰Is -CO₂R^{3 3} And R³³Represents t-butyl, R¹⁰Is -CO₂The corresponding H
Esterifying a compound. 19. The method of claim 1, substantially as described in the detailed description of the invention. 20. The herbicidal composition according to claim 13, substantially as described in the detailed description of the invention. 21. The method according to claim 14, substantially as described in the detailed description of the invention.