JPH11147866A - Aminophenol derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound hardly exhibiting a crop-damaging action against paddy rice, expressing an excellent herbicidal activity at a low dose against strongly injurious weeds such as Echinochloa oryzicola in paddy fields, and useful as a herbicide. SOLUTION: The compound of formula I [R<1> is a (halogenated) 1-6C alkyl; R<2> is H or the like; Z is nitrogen or the like; R<3> is a 1-6C alkyl or the like; (n) is 0-3; R<4> and R<5> are each H or the like; A is a group of the formula: C<=C or the like; Q is a 6-10C aryl capable of being substituted by one to five groups such as (halogenated) 1-6C alkyl groups, or the liked, for example, methyl N-[2- methyl-4-(3-phenylpro-2-pynyloxy)phenyl]carbamate, is obtained, for example, by etherifying a compound of formula II [for example, methyl N-(4-hydroxy-2- methylphenyl)carbamate] with a compound of formula III (L<1> is a releasable group) (for example, 1-phenyl-3-chloro-1-propyne) in the presence of a base in a solvent preferably at a temperature of -5 to 10 deg.C for 30 min to 5 hr.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel aminophenol derivative having excellent herbicidal activity.

[0002]

2. Description of the Related Art There has been a demand for a herbicide that selectively kills only harmful weeds without causing phytotoxicity to crops. As a result of various studies, many selective herbicides have been published, but the emergence of even better herbicides is desired.

[0003] As aminophenol derivatives, 1,1-dimethyl-3- (4-phenylpropargyloxyphenyl) urea (US Pat. No. 4,289,90) has been used.
3) and 1,1-dimethyl-3- {4- (2-methylcinnamoyloxy) phenyl} urea (JP-A-59-1)
No. 93810) is known to have field crop weeding activity.

[0004] However, these compounds are different from the present compounds in that they have a urea partial structure. In addition, while the compound of the present invention exhibits excellent herbicidal activity against barnyardgrass and is useful as a paddy field herbicide, the above-mentioned prior art compound has low potency against barnyardgrass and is not useful as a paddy field herbicide, that is, the herbicidal spectrum. From the point of
It is completely different.

[0005] N- (4-phenylpropargyloxyphenyl) is also used as an aminophenol derivative.
Amide derivatives (JP-A-8-157435) are known to have paddy field herbicidal activity.
It differs from the compound of the present application in having an amide partial structure.

[0006]

SUMMARY OF THE INVENTION The inventor of the present invention has conducted intensive studies on the synthesis and biological activity of aminophenol derivatives over many years. As a result, a novel aminophenol derivative having a structure different from that of known compounds has been obtained. The present inventors have found that they show almost no phytotoxicity to paddy rice, and show excellent herbicidal activity at a low dose in herbaceous rice, which is a highly harmful weed in paddy fields, and completed the present invention.

[0007]

The aminophenol derivative having excellent herbicidal activity of the present invention or a salt thereof is represented by the general formula (I):

[0008]

Embedded image [Wherein, R ¹ represents a C1-C6 alkyl group (the alkyl group may be substituted by a halogen atom), and R ² represents a hydrogen atom, a C1-C6 alkyl group (the alkyl group is Hydroxyl group, C1-C6 alkoxy group, C1-
It may be substituted by a C6 alkylthio group or a C1-C6 alkylsulfonyl group. ), C3 -C6 alkenyl group, a C3 -C6 alkynyl group or a benzyl group, Z is a group represented by the nitrogen atom or the formula -C (R ^3a), R ^3a is a hydrogen atom, C1 -C6 Alkyl group, C1
~C6 an alkoxy group or a halogen atom, R ³ is
A C1-C6 alkyl group, a C1-C6 alkoxy group or a halogen atom, and n represents 0, 1, 2, or 3 (however, when n is 2 or 3, each R ³ is the same or different And adjacent R ³ may be taken together to form a 5- or 6-membered ring.), R ⁴ and R ⁵
Are the same or different and each represent a hydrogen atom or a C1-C6 alkyl group, and A is a group represented by the formula -C≡C- or a formula-
C (R ⁶ ) = CH- (wherein R ⁶ is a hydrogen atom, C 1 -C
6 represents an alkyl group or a halogen atom. Q is a C6-C10 aryl group [the aryl group is a C1-C6 alkyl group (the alkyl group may be substituted with 1 to 5 same or different halogen atoms. May be substituted with 1 to 5 identical or different substituent (s) selected from the group consisting of C1-C6 alkoxy groups, phenoxy groups, halogen atoms, nitro groups and cyano groups] or at least one A heterocyclic group containing an oxygen, sulfur or nitrogen atom and having 3 to 10 ring atoms (the heterocyclic group is 1 to 4 identical or different halogen atoms, and 1 to 3 identical or different C1 ~ C
6 alkyl groups or 1 to 3 identical or different C1
It may be substituted by a C6 alkoxy group, or may be condensed with a benzene ring. ). And a salt thereof.

[0009] In the present specification, the "halogen atom" is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Preferably, it is a fluorine atom or a chlorine atom.

In the present specification, "C1-C6 alkyl" means, for example, methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, s-butyl, t-butyl, cyclobutyl, pentyl, isopentyl, 2 -Methylbutyl, neopentyl, 1-ethylpropyl, cyclopentyl, hexyl, 4-methylpentyl, 3-
Methylpentyl, 2-methylpentyl, 1-methylpentyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2, It is a linear or branched alkyl group having 1 to 6 carbon atoms, such as 3-dimethylbutyl, 2-ethylbutyl, cyclohexyl, and preferably a linear or branched alkyl group having 1 to 4 carbon atoms (C1 To C4 alkyl group), more preferably a linear or branched alkyl group having 1 to 3 carbon atoms (C1 to C3 alkyl group), more preferably a methyl group or an ethyl group, Most preferably, it is a methyl group.

In the present specification, "C3-C6 alkenyl group" means, for example, 2-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-ethyl-2-propenyl, 2-ethyl-2-propenyl, Butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 1-ethyl-2-butenyl, 3-butenyl, 1-methyl-
3-butenyl, 2-methyl-3-butenyl, 1-ethyl-3-butenyl, 2-pentenyl, 1-methyl-2-pentenyl, 2-methyl-
2-pentenyl, 3-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 4-pentenyl, 1-methyl-
A straight-chain or branched-chain alkenyl group having 3 to 6 carbon atoms, such as 4-pentenyl, 2-methyl-4-pentenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, and 5-hexenyl; Is a linear or branched alkenyl group having 3 to 5 carbon atoms (C3-C5 alkenyl group), more preferably 2-propenyl, 1-methyl-2-propenyl or 2-butenyl, Preferably, it is a 2-propenyl group.

In the present specification, "C3-C6 alkynyl group" means, for example, 2-propynyl, 1-methyl-2-propynyl, 2-butynyl, 1-methyl-2-butynyl, 1-ethyl-
2-butynyl, 3-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-ethyl-3-butynyl, 2-pentynyl, 1-methyl-2-pentynyl, 3-pentynyl, 1- Methyl-
3-pentynyl, 2-methyl-3-pentynyl, 4-pentynyl, 1-methyl-4-pentynyl, 2-methyl-4-pentynyl,
A straight-chain or branched alkynyl group having 3 to 6 carbon atoms, such as 2-hexynyl, 3-hexynyl, 4-hexynyl and 5-hexynyl, preferably a straight-chain or branched alkynyl group having 3 to 5 carbon atoms; It is a branched alkynyl group (C3-C5 alkynyl group), more preferably a 2-propynyl group.

In the present specification, "C1-C6 alkoxy" means, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, t-butoxy, pentoxy, isopentoxy, 2-methylbutoxy, Neopentoxy, 1-ethylpropoxy,
Hexyloxy, 4-methylpentoxy, 3-methylpentoxy, 2-methylpentoxy, 1-methylpentoxy, 3,3-
1 to 1 carbon atoms such as dimethylbutoxy, 2,2-dimethylbutoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,3-dimethylbutoxy, 2-ethylbutoxy 6 straight-chain or branched-chain alkoxy groups, preferably a straight-chain or branched-chain alkoxy group having 1 to 3 carbon atoms (C1-C3 alkoxy group), more preferably a methoxy group or an ethoxy group And more preferably a methoxy group.

In the present specification, the "C1-C6 alkylthio group" is, for example, methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, s-butylthio, t-butylthio, pentylthio, isopentylthio, Methylbutylthio, neopentylthio, 1-ethylpropylthio, hexylthio, 4-methylpentylthio, 3-methylpentylthio, 2-methylpentylthio, 1-methylpentylthio, 3,3-dimethylbutylthio, 2, 1-carbon such as 2-dimethylbutylthio, 1,1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,3-dimethylbutylthio, and 2-ethylbutylthio A straight-chain or branched alkylthio group having 1 to 3 carbon atoms, preferably a straight-chain or branched alkylthio group having 1 to 3 carbon atoms (C1 to C3 alkylthio group). A group),
More preferably, it is a methylthio group or an ethylthio group.

In the present specification, "C1-C6 alkylsulfonyl group" means, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, s-
Butylsulfonyl, t-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, 2-methylbutylsulfonyl, neopentylsulfonyl, 1-ethylpropylsulfonyl, hexylsulfonyl, 4-methylpentylsulfonyl, 3-methylpentylsulfonyl, 2-methylpentyl Sulfonyl, 1-methylpentylsulfonyl, 3,3-dimethylbutylsulfonyl, 2,2-dimethylbutylsulfonyl, 1,1-dimethylbutylsulfonyl, 1,2-dimethylbutylsulfonyl, 1,3-dimethylbutylsulfonyl, 2, An alkylsulfonyl group having 1 to 6 carbon atoms, such as a 3-dimethylbutylsulfonyl and 2-ethylbutylsulfonyl group, and preferably a linear or branched alkylsulfonyl group having 1 to 3 carbon atoms. And more preferably a methylsulfonyl or ethylsulfonyl group. You.

As used herein, the term "C1-C6 alkyl group substituted by a halogen atom" includes, for example, chloromethyl, dichloromethyl, trichloromethyl, 1-chloroethyl, 2-chloroethyl, 1-chloropropyl, 3-chloromethyl Propyl, 1-chlorobutyl, 4-chlorobutyl, 2,2,2-
Trichloroethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, fluorochloromethyl, bromomethyl, 1-bromoethyl, 2-bromoethyl, 1,1,1,2-tetrachloroethyl, 1, Like 1,2,2-tetrafluoroethyl, pentafluoroethyl, 2,2,3,3,3-pentafluoropropyl
A group in which 1 to 5 identical or different “halogen atoms” are bonded to the “C1 to C6 alkyl group”, preferably, for example, chloromethyl, dichloromethyl, trichloromethyl, 1-chloroethyl, Chloroethyl, 1-chloropropyl, 3-chloropropyl, 2,2,2-trichloroethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, fluorochloromethyl, bromomethyl, 1-bromoethyl , 2-bromoethyl, a C1-C3 alkyl group substituted by 1 to 3 halogen atoms, more preferably a fluoromethyl group, a chloromethyl group, a trifluoromethyl group or a 2,2,2 -A trichloroethyl group.

In the present specification, "C1-C6 alkyl group substituted by C1-C6 alkylthio group" means, for example, methylthiomethyl, ethylthiomethyl, propylthiomethyl, butylthiomethyl, t-butylthiomethyl, hexyl The above-mentioned “C1-C1” such as thiomethyl, methylthioethyl, methylthiopropyl, ethylthioethyl
One “C6 alkylthio group” is a group bonded to the above “C1 to C6 alkyl group”, and preferably has 1 to 6 carbon atoms such as methylthiomethyl, ethylthiomethyl, propylthiomethyl, methylthiopropyl and ethylthioethyl. 3
And is an alkyl group having 1 to 3 carbon atoms substituted by 2 alkylthio groups, more preferably a methylthiomethyl group or an ethylthiomethyl group.

In the present specification, "C1-C6 alkyl group substituted by C1-C6 alkylsulfonyl group" means, for example, methylsulfonylmethyl, ethylsulfonylmethyl, propylsulfonylmethyl, butylsulfonylmethyl, t-butylsulfonylmethyl , Hexylsulfonylmethyl, methylsulfonylethyl, methylsulfonylpropyl, ethylsulfonylethyl, and one of the “C1-C6 alkylsulfonyl groups” is the same as the “C1
To C6 alkyl group ", and is preferably substituted by an alkylsulfonyl group having 1 to 3 carbon atoms such as methylsulfonylmethyl, ethylsulfonylmethyl, propylsulfonylmethyl, methylsulfonylpropyl and ethylsulfonylethyl. Alkyl group having 1 to 3 carbon atoms, more preferably a methylsulfonylmethyl group or an ethylsulfonylmethyl group.

In the present specification, "C1-C6 alkyl group substituted by C1-C6 alkoxy group" means, for example, methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, s-butoxymethyl, t-butoxymethyl, Pentyloxymethyl, hexyloxymethyl,
Methoxyethyl, ethoxyethyl, propoxyethyl,
Butoxyethyl, methoxypropyl, methoxybutyl,
One of the “C1 to C6 alkoxy group” such as methoxypentyl and methoxyhexyl is a group bonded to the “C1 to C6 alkyl group”, preferably one alkoxy group having 1 to 3 carbon atoms. And is an alkyl group having 1 to 3 carbon atoms, more preferably a methoxymethyl group or an ethoxymethyl group.

In the present specification, the "C1-C6 alkyl group substituted by a hydroxyl group" is the above-mentioned "C1-C6 alkyl group" having one or two hydroxyl groups bonded, and preferably one hydroxyl group is bonded. It is the aforementioned “C1-C4 alkyl group” bonded, more preferably a hydroxymethyl group.

In the present specification, the "C6-C10 aryl group" is an aryl group having 6 to 10 carbon atoms, such as phenyl and naphthyl, and is preferably a phenyl group.

In the present specification, "a C1-C6 alkyl group (the alkyl group may be substituted by a halogen atom), a C1-C6 alkoxy group, a phenoxy group, a halogen atom, a nitro group and a cyano group. C6-substituted by 1 to 5 identical or different substituents
The “C10 aryl group” is, for example, a chlorophenyl group,
Dichlorophenyl group, bromophenyl group, nitrophenyl group, cyanophenyl group, fluorophenyl group, difluorophenyl group, trifluoromethylphenyl group, methylphenyl group, dimethylphenyl group, trimethylphenyl group, chloromethylphenyl group, methoxyphenyl group,
Methoxymethylphenyl group, pentafluorophenyl group, pentabromophenyl group, pentachlorophenyl group, pentamethylphenyl group, phenoxyphenyl group,
Chloronaphthyl group, bromonaphthyl group, fluoronaphthyl group, dichloronaphthyl group, dibromonaphthyl group, cyanonaphthyl group, nitronaphthyl group, methylnaphthyl group,
The above-mentioned “C” such as methoxynaphthyl group, dimethylnaphthyl group, dimethoxynaphthyl group, trimethylnaphthyl group, methoxymethylnaphthyl group, chloromethylnaphthyl group;
Selected from the group consisting of a "1-C6 alkyl group", the "C1-C6 alkyl group substituted by a halogen atom", the "C1-C6 alkoxy group", a phenoxy group, the "halogen atom", a nitro group and a cyano group. And the same or different substituents are 1 to 5 groups bonded to the “C6 to C10 aryl group”, preferably the “C1 to C4
Alkyl group "and the" C substituted by a halogen atom "
A phenyl group in which 1 to 5 identical or different substituents selected from the group consisting of a "1 to C4 alkyl group", the "C1 to C3 alkoxy group" and the "halogen atom" are substituted, and more preferably A methyl group, a trifluoromethyl group, a methoxy group, a phenyl group in which 1 to 5 identical or different substituents selected from the group consisting of a chlorine atom and a fluorine atom are substituted, more preferably a methylphenyl group, It is a methoxyphenyl group, a chlorophenyl group, a fluorophenyl group, a difluorophenyl group or a trifluoromethylphenyl group, and most preferably a methylphenyl group, a fluorophenyl group, a difluorophenyl group or a trifluoromethylphenyl group.

As used herein, the term "containing at least one oxygen, sulfur or nitrogen atom and having 3 to 10 ring atoms"
(The heterocyclic group is 1 to 4 identical or different halogen atoms, 1 to 3 identical or different C1 to C6 alkyl groups, or 1 to 3 identical or different C1 to May be substituted by a C6 alkoxy group,
Further, it may be condensed with a benzene ring. ) "Is, for example, oxiranyl, oxetanyl, aziridinyl, azetidinyl, thiranyl, thietanyl, 2,2-dimethyl-1,3
-Dioxanyl, furyl, thienyl, pyrrolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, imidazolyl, pyrazolyl, 5-chloro-1,3-dimethyl-4-pyrazolyl, pyranyl, pyrrolidyl, piperidyl, pyrazinyl, pyridyl, pyridazinyl, pyrimidinyl, benzofuranyl , Benzothiophenyl, benzothiazolyl, benzoxazolyl, indolyl, quinolyl,
Isoquinolyl, quinazolyl, quinoxalinyl, naphthyridinyl, xanthenyl, tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, thiazolidinyl, imidazolidinyl, imidazolinyl, oxazolinyl, pyrazolidinyl, piperazinyl, tetrahydropyrimidinyl, morpholinyl, indolinyl, indolinyl, quinolinyl, indolinyl, indolinyl An unsaturated or partially or completely saturated heterocyclic group such as -quinolyl, containing at least one oxygen, sulfur or nitrogen atom and having 3 to 10 ring atoms, wherein the heterocyclic group is 1 to 4 identical or different “halogen atoms”, 1 to 3 identical or different “C1
Or a heterocyclic group which may be substituted with 1 to 3 identical or different “C1 to C6 alkoxy groups”, and which may be condensed with a benzene ring. 1 to 4 identical or different “halogen atoms”, 1 to 3 identical or different “C
A C 1 -C 4 alkyl group ”or one or three identical or different“ C 1 -C 3 alkoxy groups ”, which contains at least one oxygen, sulfur or nitrogen atom and has 3 to 6 ring atoms. More preferably, furyl, thienyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, imidazolyl,
A pyrazolyl, pyranyl, pyrazinyl, pyridyl, pyridazinyl, pyrimidinyl, benzofuranyl, benzoxazolyl or benzothiazolyl group, more preferably,
It is a furyl, thienyl or pyridyl group.

The compound (I) of the present invention can be converted into salts such as, for example, sulfates, hydrochlorides, nitrates and phosphates. These salts are included in the present invention as long as they can be used as agricultural and horticultural herbicides.

The wettable powder of the compound of the present invention is also included in the present invention.

Some of the compounds of the present invention have an asymmetric carbon. In such a case, the present invention includes a mixture of one kind of optically active substance and several kinds of optically active substances at an arbitrary ratio. . (A) In the general formula (I), R ¹ is preferably a C1 to C4 alkyl group (the alkyl group may be substituted by a halogen atom), and more preferably a methyl group. Or an ethyl group (the methyl group or the ethyl group may be substituted by a chlorine atom), and more preferably a methyl group. (B) In the general formula (I), R ² is preferably a hydrogen atom, a C1-C4 alkyl group (the alkyl group may be substituted with a hydroxyl group or a C1-C4 alkoxy group). And more preferably a hydrogen atom or a hydroxymethyl group, and even more preferably a hydrogen atom. (C) In the general formula (I), Z is preferably
It is a nitrogen atom or a group represented by the formula -CH, more preferably a group represented by the formula group -CH. (D) In the general formula (I), R ³ is preferably a C1-C4 alkyl group, a C1-C3 alkoxy group or a halogen atom, more preferably a methyl group, a methoxy group or a fluorine atom. And more preferably a methyl group.

In the above formula (I), n is preferably 0 or 1, and more preferably 1. (E) In the general formula (I), R ⁴ and R ⁵ are preferably the same or different and are each a hydrogen atom or a methyl group, and more preferably both are hydrogen atoms. (F) In the general formula (I), A is preferably
A group represented by the formula —C≡C— or a formula —C (R ⁶ ) ＝ CH—
(Wherein, R ⁶ represents a hydrogen atom, a C1-C4 alkyl group or a halogen atom), and more preferably, a group represented by the formula -C≡C- or a group represented by the formula- C (R ⁶ ) =
CH- (wherein R ⁶ represents a hydrogen atom or a chlorine atom), and more preferably a group represented by the formula -C≡C
It is a group represented by-. (G) In the general formula (I), Q is preferably
A phenyl group [the phenyl group is a C1 to C4 alkyl group (the alkyl group may be substituted by a halogen atom), a C1 to C3 alkoxy group, and one to five identical groups selected from a halogen atom; Or it may be substituted by a different substituent. Or 3 to 6 ring atoms containing at least one oxygen, sulfur or nitrogen atom
(The heterocyclic group is 1 to 4 identical or different halogen atoms, 1 to 3 identical or different C1 to C4 alkyl groups, or 1 to 3 identical or different C1 to May be substituted by a C3 alkoxy group,
Further, it may be condensed with a benzene ring. ). And more preferably a phenyl group which may be substituted by 1 to 5 identical or different substituents selected from the group consisting of a methyl group, a trifluoromethyl group, a methoxy group, a chlorine atom and a fluorine atom , A furyl group, a thienyl group or a pyridyl group, more preferably a methylphenyl group, a fluorophenyl group, a difluorophenyl group, a trifluoromethylphenyl group, a furyl group, a thienyl group or a pyridyl group.

In the above general formula (I), (1) preferably (1a) R ¹ is preferably C1
-C4 alkyl group (the alkyl group may be substituted by a halogen atom), and (1b) R ² is
A hydrogen atom, a C1-C4 alkyl group (the alkyl group
It may be substituted by a hydroxyl group or a C1-C4 alkoxy group. And (1c) Z is a nitrogen atom or a formula -C
H is a group represented by (1d) R ³ is a group represented by C1 to C4
An alkyl group, a C1-C3 alkoxy group or a halogen atom, n is 0 or 1, and (1e) R ⁴ and R ⁵
Are preferably the same or different and each is a hydrogen atom or a methyl group, and (1f) A is a group represented by the formula —C≡C— or a formula —C (R ⁶ ) ＝ CH— (wherein , R ⁶ are a hydrogen atom,
It represents a C1 to C4 alkyl group or a halogen atom. Q is a phenyl group [the phenyl group is a C1 to C4 alkyl group (the alkyl group may be substituted by a halogen atom);
It may be substituted by 1 to 5 identical or different substituents selected from the group consisting of a C3 alkoxy group and a halogen atom. Or a heterocyclic group having at least one oxygen, sulfur or nitrogen atom and having 3 to 6 ring atoms (the heterocyclic group is preferably 1 to 4 identical or different halogen atoms, 1 to 3 Same or different C1 to C4 alkyl groups or 1 to 3 same or different C1 to C3
It may be substituted by an alkoxy group, or may be condensed with a benzene ring. ). ]. (2) More preferably, (2a) R ¹ is a methyl group or an ethyl group (the methyl group or the ethyl group may be substituted by a chlorine atom), and (2b) R ² is
A hydrogen atom or a hydroxymethyl group, and (2c) Z
Is a group represented by the formula —CH, and (2d) R ³ is
A methyl group, a methoxy group or a fluorine atom;
(2e) R ⁴ and R ⁵ are both hydrogen atoms, and (2f) A is a group represented by the formula —C≡C— or a formula —C (R ⁶ ) ＝ CH— (wherein , R ⁶ represents a hydrogen atom or a chlorine atom.), And (2g) Q is
A phenyl group, a furyl group, a thienyl group or a pyridyl group which may be substituted by 1 to 5 identical or different substituents selected from the group consisting of a methyl group, a trifluoromethyl group, a methoxy group, a chlorine atom and a fluorine atom It is. (3) More preferably, (3a) R ¹ is a methyl group, (3b) R ² is a hydrogen atom, and (3c)
Z is a group represented by the formula —CH, and (3d) R
³ is a methyl group, n is 1 and (3e) R ⁴
And R ⁵ are both hydrogen atoms, (3f) A is a group represented by the formula —C≡C—, (3g) Q is a methylphenyl group, a fluorophenyl group, a difluorophenyl group, A fluoromethylphenyl group, a furyl group, a thienyl group or a pyridyl group. (4) Most preferably, methyl N- {2-methyl-4
-(3-phenylpro-2-pinyloxy) phenyl}
Carbamate (Compound No. 3.2), methyl N- ｛2
-(3-phenylpro-2-pinyloxy) pyridin-5
-Nyl} carbamate (Compound No. 3.35), methyl N- {4- (3-phenylpro-2-pinyloxy)
Phenyl} carbamate (Compound No. 1.1), methyl N- {2-methoxy-4- (3-phenylpro-2-)
Pinyloxy) phenyl} carbamate (Compound No. 3.21), methyl N- {2-fluoro-4- (3-
Phenylpro-2-pinyloxy) phenyl} carbamate (compound number 3.7), methyl N- {2-chloro-4- (3-phenylpro-2-pinyloxy) phenyl} carbamate (compound number 3.8), methyl N-
[4- {3- (4-methylphenyl) pro-2-pinyloxy} phenyl] carbamate (Compound No. 5.
3), methyl N- [4- {3- (2-fluorophenyl) pro-2-pinyloxy} phenyl] carbamate (Compound No. 5.4), methyl N- [4- {3- (3
-Fluorophenyl) pro-2-pinyloxy {phenyl] carbamate (Compound No. 5.5), methyl N-
[4- {3- (4-fluorophenyl) pro-2-pinyloxy} phenyl] carbamate (Compound No. 5.
6), methyl N- [4- {3- (2,4-difluorophenyl) pro-2-pinyloxy} phenyl] carbamate (compound number 5.8), methyl N- [4- {3
-(2-methoxyphenyl) pro-2-pinyloxy}
Phenyl] carbamate (Compound No. 5.34), methyl N- [4- {3- (2-furyl) pro-2-pinyloxy} phenyl] carbamate (Compound No. 5.5)
0), methyl N- [4- {3- (2-thienyl) pro-2-pinyloxy} phenyl] carbamate (Compound No. 5.60), methyl N- [4- {3- (3-pyridyl) pro- 2-Pinyloxy {phenyl] carbamate (Compound No. 5.71), Methyl N- [2-methyl-4- {3- (2-methylphenyl) pro-2-pinyloxy} phenyl] carbamate (Compound No. 8.
1), methyl N- [4- {3- (2-fluorophenyl) pro-2-pinyloxy} -2-methylphenyl]
Carbamate (compound number 8.4), methyl N- [4
-{3- (3-fluorophenyl) pro-2-pinyloxy} -2-methylphenyl] carbamate (Compound No. 8.5), methyl N- [4- {3- (4-fluorophenyl) pro-2- Pinyloxy {-2-methylphenyl] carbamate (Compound No. 8.6), methyl N
-[4- {3- (2,4-difluorophenyl) pro-
2-Pinyloxy} -2-methylphenyl] carbamate (Compound No. 8.8), methyl N- [4- {3-
(2-methoxyphenyl) pro-2-pinyloxy}-
2-methylphenyl] carbamate (compound number 8.3
4), methyl N- [4- {3- (3-methoxyphenyl) pro-2-pinyloxy} -2-methylphenyl]
Carbamate (compound number 8.35), methyl N-
[4- {3- (4-methoxyphenyl) pro-2-pinyloxy} -2-methylphenyl] carbamate (compound number 8.36), methyl N- [2-methyl-4-
{3- (3-trifluoromethylphenyl) pro-2-
Pinyloxy {phenyl] carbamate (compound number 8.48), methyl N- [2-methyl-4- {3-
(4-trifluoromethylphenyl) pro-2-pinyloxydiphenyl] carbamate (Compound No. 8.4
9), methyl N- [4- {3- (2-furyl) pro-
2-Pinyloxy} -2-methylphenyl] carbamate (Compound No. 8.50), methyl N- [4- {3-
(3-furyl) pro-2-pinyloxy {-2-methylphenyl] carbamate (Compound No. 8.51), methyl N- [2-methyl-4- {3- (2-thienyl) pro-2-pinyloxy} Phenyl] carbamate (compound number 8.60), methyl N- [2-methyl-4-
{3- (3-pyridyl) pro-2-pinyloxy} phenyl] carbamate (Compound No. 8.71) or methyl N- [4- {3- (2-fluorophenyl) pro-2]
[Penyloxydiphenyl] carbamate (Compound No. 6.4) and salts thereof.

Representative compounds of the present invention are shown in Table 1 below, but the present invention is not limited to these compounds.

Hereinafter, "Me" is a methyl group, "Et" is an ethyl group, "Pr" is a propyl group, "iPr" is an isopropyl group, "Bu" is a butyl group, and "tBu" is a tert group. A butyl group, “Ph” a phenyl group, “F
"ur" represents a furyl group, "Thio" represents a thienyl group,
“Pyr” represents a pyridyl group, “Pyz” represents a pyrazolyl group, “Oxaz” represents an oxazolyl group, “Thia” represents a thiazolyl group, “BFur” represents a benzofuranyl group,
"BThio" represents a benzothiophenyl group, and "BOxa
“z” represents a benzoxazolyl group, and “BThia” represents a benzothiazolyl group.

R^ThreeAnd Q, the number before the substituent
The letter indicates the position of the substituent, and the subscript
The numbers in the following indicate the number of substitutions of the substituent. For example, 2-
CF _ThreeIs a trifluoromethyl group substituted at the 2-position,
2,4-F_TwoIs a 2,4-difluoro group.

In the table below, the presence of H in the column of (R ³ ) _n indicates that n is 0.

[0033]

[Table 1]

[0034]

Embedded image ────────────────────────────────── Compound number R ¹ R ² (R ³ ) _n ZR ⁴ R ⁵ A Q ────────────────────────────────── 1.1 Me HH CH HHC≡C Ph 1.2 Et HH CH HHC≡C Ph 1.3 Pr HH CH HHC≡C Ph 1.4 Bu HH CH HHC≡C Ph 1.5 iPr HH CH HHC≡C Ph 1.6 tBu HH CH HHC≡C Ph 1.11 Cl ₃ CCH ₂ HH CH HHC≡C Ph 2.1 Me Me H CH HHC ≡C Ph 2.2 Me CH ₂ CH = CH ₂ H CH HHC≡C Ph 2.3 Me CH ₂ C≡CH H CH HHC≡C Ph 2.4 Me CH ₂ Ph H CH HHC≡C Ph 2.5 Me CH ₂ SMe H CH HHC≡ C Ph 2.6 Me CH ₂ SO ₂ Me H CH HHC≡C Ph 2.7 Me CH ₂ OH H CH HHC≡C Ph 2.8 Me CH ₂ OMe H CH HHC≡C Ph 3.1 Me H 3-Me CH HHC≡C Ph 3.2 Me H 2-Me CH HHC≡C Ph 3.3 Me H 2,3-Me ₂ CH HHC≡C Ph 3.4 Me H 2-Me CMe HHC≡C Ph 3.5 Me H 3-Me CMe HHC≡C Ph 3.6 Me H 2, 6-Me ₂ CH HHC≡C Ph 3.7 Me H 2-F CH HHC≡C Ph 3.8 Me H 2-Cl CH HHC≡C Ph 3.9 Me H 3-F CH HHC≡C Ph 3.10 Me H 3-Cl CH HHC ≡C Ph 3.11 Me H 2,3-F ₂ C H HHC≡C Ph 3.12 Me H 2,3-Cl ₂ CH HHC≡C Ph 3.17 Me H 2,6-F ₂ CH HHC≡C Ph 3.18 Me H 2,6-Cl ₂ CH HHC≡C Ph 3.21 Me H 2-MeO CH HHC≡C Ph 3.22 Me H 3-MeO CH HHC≡C Ph 3.23 Me H 2-EtO CH HHC≡C Ph 3.24 Me H 3-EtO CH HHC≡C Ph 3.25 Me H 2-PrO CH HHC≡ C Ph 3.26 Me H 3-PrO CH HHC≡C Ph 3.27 Me H 2-iPrO CH HHC≡C Ph 3.28 Me H 3-iPrO CH HHC≡C Ph 3.29 Me H 2-F CF HHC≡C Ph 3.30 Me H 2 -Cl CCl HHC≡C Ph 3.31 Me H 3-F CF HHC≡C Ph 3.32 Me H 3-Cl CCl HHC≡C Ph 3.33 Me H 2-Me CCl HHC≡C Ph 3.34 Me H 2-OMe CCl HHC≡C Ph 3.35 Me HHNHHC≡C Ph 3.36 Me H 2-Me NHHC≡C Ph 3.37 Me H 3-Me NHHC≡C Ph 3.38 Me H 6-Me NHHC≡C Ph 3.39 Me H 2-MeO NHHC≡C Ph 3.40 Me H 3-MeO NHHC≡C Ph 3.41 Me H 6-MeO NHHC≡C Ph 3.42 Me H 2-Cl NHHC≡C Ph 3.43 Me H 3-Cl NHHC≡C Ph 3.44 Me H 6-Cl NHHC≡C Ph 3.45 Me H CHCHCHCH NHHC≡C Ph 3.46 Me H CHCHCHN NHHC≡C Ph 4.1 Me HH CH Me HC≡C Ph 4.2 Me HH CH Et HC≡C Ph 4.3 Me HH CH Me Me C≡C Ph 4.4 Me H 2-Me CH Me HC ≡C Ph 4.5 Me H 2-Me CH Me Me C≡C Ph 4.6 Me H 3-Me CH Me HC≡C Ph 4.7 Me H 3-Me CH Me Me C≡C Ph 4.8 Me HHN Me HC≡C Ph 4.9 Me HHN Me Me C≡C Ph 4.10 Me H 2-Me N Me HC≡C Ph 4.11 Me H 2-Me N Me Me C≡C Ph 4.12 Me H 3-Me N Me HC≡C Ph 4.13 Me H 3-Me N Me Me C≡C Ph 4.14 Me HH CH Et Et C≡ C Ph 5.1 Me HH CH HHC≡C 2-Me-Ph 5.2 Me HH CH HHC≡C 3-Me-Ph 5.3 Me HH CH HHC≡C 4-Me-Ph 5.4 Me HH CH HHC≡C 2-F-Ph 5.5 Me HH CH HHC≡C 3-F-Ph 5.6 Me HH CH HHC≡C 4-F-Ph 5.7 Me HH CH HHC≡C 2,3-F ₂ -Ph 5.8 Me HH CH HHC≡C 2,4- F ₂ -Ph 5.9 Me HH CH HHC≡C 2,5-F ₂ -Ph 5.10 Me HH CH HHC≡C 2,6-F ₂ -Ph 5.11 Me HH CH HHC≡C 3,4-F ₂ -Ph 5.12 Me HH CH HHC≡C 3,5-F ₂ -Ph 5.13 Me HH CH HHC≡C 2,3,5-F ₃ -Ph 5.14 Me HH CH HHC≡C 2,4,6-F ₃ -Ph 5.15 Me _{HH CH HHC≡C 2,4,5-F 3 -Ph} 5.16 Me HH CH HHC≡C 2,3,6-F 3 -Ph 5.17 Me HH CH HHC≡C 2,3,5,6-F 4 - Ph 5.18 Me HH CH HHC≡C 2,3,4,5,6-F ₅ -Ph 5.19 Me HH CH HHC≡C 2-Cl-Ph 5.20 Me HH CH HHC≡C 3-Cl-Ph 5.21 Me HH CH HHC≡C 4-Cl-Ph 5.22 Me HH CH HHC≡C 2,3-Cl ₂ -Ph 5.23 Me HH CH H HC≡C 2,4-Cl ₂ -Ph 5.24 Me HH CH HHC≡C 2,5-Cl ₂ -Ph 5.25 Me HH CH HHC≡C 2,6-Cl ₂ -Ph 5.26 Me HH CH HHC≡C 3, 4-Cl ₂ -Ph 5.27 Me HH CH HHC≡C 3,5-Cl ₂ -Ph 5.28 Me HH CH HHC≡C 2,3,5-Cl ₃ -Ph 5.29 Me HH CH HHC≡C 2,4,6 -Cl ₃ -Ph 5.30 Me HH CH HHC≡C 2,4,5-Cl ₃ -Ph 5.31 Me HH CH HHC≡C 2,3,6-Cl ₃ -Ph 5.32 Me HH CH HHC≡C 2-Cl, 4-F-Ph 5.33 Me HH CH HHC≡C 2-F, 6-Cl-Ph 5.34 Me HH CH HHC≡C 2-OMe-Ph 5.35 Me HH CH HHC≡C 3-OMe-Ph 5.36 Me HH CH HHC ≡C 4-OMe-Ph 5.37 Me HH CH HHC≡C 2,3- (OMe) ₂ -Ph 5.38 Me HH CH HHC≡C 2,4- (OMe) ₂ -Ph 5.39 Me HH CH HHC≡C 2, 5- (OMe) ₂ -Ph 5.40 Me HH CH HHC≡C 2,6- (OMe) ₂ -Ph 5.41 Me HH CH HHC≡C 3,4- (OMe) ₂ -Ph 5.42 Me HH CH HHC≡C 3 , 5- (OMe) ₂ -Ph 5.43 Me HH CH HHC≡C 2-OEt-Ph 5.44 Me HH CH HHC≡C 4-OEt-Ph 5.45 Me HH CH HHC≡C 3-OPh-Ph 5.46 Me HH CH HHC ≡C 4-OPh-Ph 5.47 Me HH CH HHC≡C 2-CF ₃ -Ph 5.48 Me HH CH HHC≡C 3-CF ₃ -Ph 5.49 Me HH CH HHC≡C 4-CF ₃ -Ph 5.50 Me HH CH HHC≡C 2-Fur 5.51 Me HH CH HHC≡C 3-Fur 5.52 Me HH CH HHC≡C 5- Me ₂ -Fur 5.53 Me HH CH HHC≡C 3-Me ₂ -Fur 5.54 Me HH CH HHC≡C 5-Me-3-Fur 5.55 Me HH CH HHC≡C 2-Me-3-Fur 5.56 Me HH CH HHC ≡C 5-MeO-2-Fur 5.57 Me HH CH HHC≡C 3-MeO-2-Fur 5.58 Me HH CH HHC≡C 5-MeO-3-Fur 5.59 Me HH CH HHC≡C 2-MeO-3- Fur 5.60 Me HH CH HHC≡C 2-Thio 5.61 Me HH CH HHC≡C 3-Thio 5.62 Me HH CH HHC≡C 5-Me-2-Thio 5.63 Me HH CH HHC≡C 3-Me-2-Thio 5.64 Me HH CH HHC≡C 5-Me-3-Thio 5.65 Me HH CH HHC≡C 2-Me-3-Thio 5.66 Me HH CH HHC≡C 5-MeO-2-Thio 5.67 Me HH CH HHC≡C 3- MeO-2-Thio 5.68 Me HH CH HHC≡C 5-MeO-3-Thio 5.69 Me HH CH HHC≡C 2-MeO-3-Thio 5.70 Me HH CH HHC≡C 2-Pyr 5.71 Me HH CH HHC≡C 3-Pyr 5.72 Me HH CH HHC≡C 4-Pyr 5.73 Me HH CH HHC≡C 3-Me ₂ -Pyr 5.74 Me HH CH HHC≡C 4-Me ₂ -Pyr 5.75 Me HH CH HHC≡C 5-Me ₂ -Pyr 5.76 Me HH CH HHC≡C 6-Me ₂ -Pyr 5.77 Me HH CH HHC≡C 3-MeO-2-Pyr 5.78 Me HH CH HHC≡C 4-MeO-2-Pyr 5.79 Me HH CH HHC≡C 5-MeO-2-Pyr 5.80 Me HH CH HHC≡C 6-MeO-2-Pyr 5.81 Me HH CH HHC≡C 3-Pyz 5.82 Me HH CH HHC≡C 4-Pyz 5.83 Me HH CH HHC≡C 5-Pyz 5.84 Me HH CH HHC≡C 2-Oxaz 5.85 Me HH CH HHC≡C 4-Oxaz 5.86 Me HH CH HHC≡C 5-Oxaz 5.87 Me HH CH HHC≡C 2-Thiaz 5.88 Me HH CH HHC≡C 4-Thiaz 5.89 Me HH CH HHC≡C 5-Thiaz 5.90 Me HH CH HHC≡C 2-BFur 5.91 Me HH CH HHC≡C 3-BFur 5.92 Me HH CH HHC≡C 2-BThio 5.93 Me HH CH HHC≡C 3-BThio 5.94 Me HH CH HHC≡C 2-BOxaz 5.95 Me HH CH HHC≡C 2-BThiaz 8.1 Me H 2-Me CH HHC≡C 2-Me-Ph 8.2 Me H 2-Me CH HHC≡C 3-Me-Ph 8.3 Me H 2-Me CH HHC≡C 4-Me-Ph 8.4 Me H 2-Me CH HHC≡C 2-F-Ph 8.5 Me H 2-Me CH HHC≡C 3- F-Ph 8.6 Me H 2-Me CH HHC≡C 4-F-Ph 8.7 Me H 2-Me CH HHC≡C 2,3-F ₂ -Ph 8.8 Me H 2-Me CH HHC≡C 2,4- F ₂ -Ph 8.9 Me H 2-Me CH HHC≡C 2,5-F ₂ -Ph 8.10 Me H 2-Me CH HHC≡C 2,6-F ₂ -Ph 8.11 Me H 2-Me CH HHC≡C 3,4-F ₂ -Ph 8.12 Me H 2-Me CH HHC≡C 3,5-F ₂ -Ph 8.13 Me H 2-Me CH HHC≡C 2,3,5-F ₃ -Ph 8.14 Me H 2 -Me CH HHC≡C 2,4,6-F ₃ -Ph 8.15 Me H 2-Me CH HHC≡C 2,4,5-F ₃ -Ph 8.16 Me H 2-Me CH HHC≡C 2,3, 6-F ₃ -Ph 8.17 Me H 2-Me CH HHC≡C 2,3,5,6-F ₄ -Ph 8. 18 Me H 2-Me CH HHC≡C 2,3,4,5,6-F ₅ -Ph 8.19 Me H 2-Me CH HHC≡C 2-Cl-Ph 8.20 Me H 2-Me CH HHC≡C 3 -Cl-Ph 8.21 Me H 2-Me CH HHC≡C 4-Cl-Ph 8.22 Me H 2-Me CH HHC≡C 2,3-Cl ₂ -Ph 8.23 Me H 2-Me CH HHC≡C 2,4 -Cl ₂ -Ph 8.24 Me H 2-Me CH HHC≡C 2,5-Cl ₂ -Ph 8.25 Me H 2-Me CH HHC≡C 2,6-Cl ₂ -Ph 8.26 Me H 2-Me CH HHC≡ C 3,4-Cl ₂ -Ph 8.27 Me H 2-Me CH HHC≡C 3,5-Cl ₂ -Ph 8.28 Me H 2-Me CH HHC≡C 2,3,5-Cl ₃ -Ph 8.29 Me H 2-Me CH HHC≡C 2,4,6-Cl ₃ -Ph 8.30 Me H 2-Me CH HHC≡C 2,4,5-Cl ₃ -Ph 8.31 Me H 2-Me CH HHC≡C 2,3 , 6-Cl ₃ -Ph 8.32 Me H 2-Me CH HHC≡C 2-Cl, 4-F-Ph 8.33 Me H 2-Me CH HHC≡C 2-F, 6-Cl-Ph 8.34 Me H 2- Me CH HHC≡C 2-OMe-Ph 8.35 Me H 2-Me CH HHC≡C 3-OMe-Ph 8.36 Me H 2-Me CH HHC≡C 4-OMe-Ph 8.37 Me H 2-Me CH HHC≡C 2,3- (OMe) ₂ -Ph 8.38 Me H 2-Me CH HHC≡C 2,4- (OMe) ₂ -Ph 8.39 Me H 2-Me CH HHC≡C 2,5- (OMe) ₂ -Ph 8.40 Me H 2-Me CH HHC≡C 2,6- (OMe) ₂ -Ph 8.41 Me H 2-Me CH HHC≡C 3,4- (OMe) ₂ -Ph 8.42 Me H 2-Me CH HHC≡C 3,5- (OMe) ₂ -Ph 8.43 Me H 2-Me CH HHC≡C 2-OEt-Ph 8.44 Me H 2-Me CH HHC≡C 4-OEt-Ph 8.45 Me H 2-Me CH HHC≡C 3-OPh-Ph 8.46 Me H 2-Me CH HHC≡C 4-OPh-Ph 8.47 Me H 2-Me CH HHC≡C 2-CF ₃ -Ph 8.48 Me H 2-Me CH HHC≡C 3-CF ₃ -Ph 8.49 Me H 2-Me CH HHC≡C 4-CF ₃ -Ph 8.50 Me H 2-Me CH HHC≡C 2-Fur 8.51 Me H 2-Me CH HHC≡C 3-Fur 8.52 Me H 2-Me CH HHC≡C 5-Me-2-Fur 8.53 Me H 2-Me CH HHC≡ C 3-Me-2-Fur 8.54 Me H 2-Me CH HHC≡C 5-Me-3-Fur 8.55 Me H 2-Me CH HHC≡C 2-Me-3-Fur 8.56 Me H 2-Me CH HHC ≡C 5-MeO-2-Fur 8.57 Me H 2-Me CH HHC≡C 3-MeO-2-Fur 8.58 Me H 2-Me CH HHC≡C 5-MeO-3-Fur 8.59 Me H 2-Me CH HHC≡C 2-MeO-3-Fur 8.60 Me H 2-Me CH HHC≡C 2-Thio 8.61 Me H 2-Me CH HHC≡C 3-Thio 8.62 Me H 2-Me CH HHC≡C 5-Me- 2-Thio 8.63 Me H 2-Me CH HHC≡C 3-Me-2-Thio 8.64 Me H 2-Me CH HHC≡C 5-Me-3-Thio 8.65 Me H 2-Me CH HHC≡C 2-Me -3-Thio 8.66 Me H 2-Me CH HHC≡C 5-MeO-2-Thio 8.67 Me H 2-Me CH HHC≡C 3-MeO-2-Thio 8.68 Me H 2-Me CH HHC≡C 5- MeO-3-Thio 8.69 Me H 2-Me CH HHC≡C 2-MeO-3-Thio 8.70 Me H 2-Me CH HHC≡C 2-Pyr 8.71 Me H 2-Me CH HHC≡C 3-Pyr 8.72 Me H 2-Me CH HHC≡C 4-Pyr 8.73 Me H 2-Me CH HHC≡C 3-Me-2-Pyr 8.74 Me H 2-Me CH HHC ≡C 4-Me-2-Pyr 8.75 Me H 2-Me CH HHC≡C 5-Me-2-Pyr 8.76 Me H 2-Me CH HHC≡C 6-Me-2-Pyr 8.77 Me H 2-Me CH HHC≡C 3-MeO-2-Pyr 8.78 Me H 2-Me CH HHC≡C 4-MeO-2-Pyr 8.79 Me H 2-Me CH HHC≡C 5-MeO-2-Pyr 8.80 Me H 2-Me CH HHC≡C 6-MeO-2-Pyr 8.81 Me H 2-Me CH HHC≡C 3-Pyz 8.82 Me H 2-Me CH HHC≡C 4-Pyz 8.83 Me H 2-Me CH HHC≡C 5-Pyz 8.84 Me H 2-Me CH HHC≡C 2-Oxaz 8.85 Me H 2-Me CH HHC≡C 4-Oxaz 8.86 Me H 2-Me CH HHC≡C 5-Oxaz 8.87 Me H 2-Me CH HHC≡C 2 -Thiaz 8.88 Me H 2-Me CH HHC≡C 4-Thiaz 8.89 Me H 2-Me CH HHC≡C 5-Thiaz 8.90 Me H 2-Me CH HHC≡C 2-BFur 8.91 Me H 2-Me CH HHC≡ C 3-BFur 8.92 Me H 2-Me CH HHC≡C 2-BThio 8.93 Me H 2-Me CH HHC≡C 3-BThio 8.94 Me H 2-Me CH HHC≡C 2-BOxaz 8.95 Me H 2-Me CH HHC≡C 2-BThiaz 6.1 Me HH CH HH CH = CH Ph 6.2 Me HH CH HH CH = CH 2-F-Ph 6.3 Me HH CH HH CH = CH 3-F-Ph 6.4 Me HH CH HH CH = CH 4 -F-Ph 6.5 Me HH CH HH CH = CH 2,3-F ₂ -Ph 6.6 Me HH CH HH CH = CH 2,4-F ₂ -Ph 6.7 Me HH CH HH CH = CH 2,5-F ₂ -Ph 6.8 Me HH CH HH CH = CH 2,6-F _2- Ph 6.9 Me HH CH HH CH = CH 3,4-F ₂ -Ph 6.10 Me HH CH HH CH = CH 3,5-F ₂ -Ph 6.11 Me HH CH HH CH = CH 2,3,5-F _3- Ph 6.12 Me HH CH HH CH = CH 2,4,6-F ₃ -Ph 6.13 Me HH CH HH CH = CH 2,4,5-F ₃ -Ph 6.14 Me HH CH HH CH = CH 2,3,6 -F ₃ -Ph 6.15 Me HH CH HH CH = CH 2,3,5,6-F ₄ -Ph 6.16 Me HH CH HH CH = CH 2,3,4,5,6-F ₅ -Ph 6.17 Me HH CH HH CH = CH 2-Cl-Ph 6.18 Me HH CH HH CH = CH 3-Cl-Ph 6.19 Me HH CH HH CH = CH 4-Cl-Ph 6.20 Me HH CH HH CH = CH 2,3-Cl ₂ -Ph 6.21 Me HH CH HH CH = CH 2,4-Cl ₂ -Ph 6.22 Me HH CH HH CH = CH 2,5-Cl ₂ -Ph 6.23 Me HH CH HH CH = CH 2,6-Cl ₂ -Ph 6.24 Me HH CH HH CH = CH 3,4-Cl ₂ -Ph 6.25 Me HH CH HH CH = CH 3,5-Cl ₂ -Ph 6.26 Me HH CH HH CH = CH 2,3,5-Cl ₃ -Ph 6.27 Me HH CH HH CH = CH 2,4,6-Cl ₃ -Ph 6.28 Me HH CH HH CH = CH 2,4,5-Cl ₃ -Ph 6.29 Me HH CH HH CH = CH 2,3,6- Cl ₃ -Ph 6.30 Me HH CH HH CH = CH 2-Cl, 4-F-Ph 6.31 Me HH CH HH CH = CH 2-F, 6-Cl-Ph 6.32 Me HH CH HH CH = CH 2-Fur 6.33 Me HH CH HH CH = CH 3-Fur 6.34 M e HH CH HH CH = CH 5-Me-2-Fur 6.35 Me HH CH HH CH = CH 3-Me-2-Fur 6.36 Me HH CH HH CH = CH 5-Me-3-Fur 6.37 Me HH CH HH CH = CH 2-Me-3-Fur 6.38 Me HH CH HH CH = CH 2-Thio 6.39 Me HH CH HH CH = CH 3-Thio 6.40 Me HH CH HH CH = CH 2-Pyr 6.41 Me HH CH HH CH = CH 3-Pyr 6.42 Me HH CH HH CH = CH 4-Pyr 6.43 Me HH CH HH CH = CH 3-Me-2-Pyr 6.44 Me HH CH HH CH = CH 4-Me-2-Pyr 6.45 Me HH CH HH CH = CH 5-Me-2-Pyr 6.46 Me HH CH HH CH = CH 6-Me-2-Pyr 6.47 Me HH CH HH CH = CH 3-Pyz 6.48 Me HH CH HH CH = CH 4-Pyz 6.49 Me HH CH HH CH = CH 5-Pyz 6.50 Me HH CH HH CH = CH 2-Oxaz 6.51 Me HH CH HH CH = CH 4-Oxaz 6.52 Me HH CH HH CH = CH 5-Oxaz 6.53 Me HH CH HH CH = CH 2- Thiaz 6.54 Me HH CH HH CH = CH 4-Thiaz 6.55 Me HH CH HH CH = CH 5-Thiaz 6.56 Me HH CH HH CH = CH 2-BFur 6.57 Me HH CH HH CH = CH 3-BFur 6.58 Me HH CH HH CH = CH 2-BThio 6.59 Me HH CH HH CH = CH 3-BThio 6.60 Me HH CH HH CH = CH 2-BOxaz 6.61 Me HH CH HH CH = CH 2-BThiaz 7.1 Me HH CH HH CCl = CH Ph 7.2 Me Me H CH HH CCl = CH Ph 7.3 Me HH CH HH CCl = CH 2-F-Ph 7.4 Me HH CH HH CCl = CH 3-F-Ph 7.5 Me HH CH HH CC l = CH 4-F-Ph 7.6 Me HH CH HH CCl = CH 2,3-F ₂ -Ph 7.7 Me HH CH HH CCl = CH 2,4-F ₂ -Ph 7.8 Me HH CH HH CCl = CH 2, 5-F ₂ -Ph 7.9 Me HH CH HH CCl = CH 2,6-F ₂ -Ph 7.10 Me HH CH HH CCl = CH 3,4-F ₂ -Ph 7.11 Me HH CH HH CCl = CH 3,5- F ₂ -Ph 7.12 Me HH CH HH CCl = CH 2-Cl-Ph 7.13 Me HH CH HH CCl = CH 3-Cl-Ph 7.14 Me HH CH HH CCl = CH 4-Cl-Ph 7.15 Me Me H CH HH CCl = CH 4-Cl-Ph 7.16 Me HH CH HH CCl = CH 2,3-Cl ₂ -Ph 7.17 Me HH CH HH CCl = CH 2,4-Cl ₂ -Ph 7.18 Me HH CH HH CCl = CH 2,5 -Cl ₂ -Ph 7.19 Me HH CH HH CCl = CH 2,6-Cl ₂ -Ph 7.20 Me HH CH HH CCl = CH 3,4-Cl ₂ -Ph 7.21 Me HH CH HH CCl = CH 3,5-Cl ₂ -Ph 7.22 Me HH CH HH CCl = CH 2-Me-Ph 7.23 Me HH CH HH CCl = CH 3-Me-Ph 7.24 Me HH CH HH CCl = CH 4-Me-Ph 7.25 Me Me H CH HH CCl = CH 4-Me-Ph 7.26 Me HH CH HH CCl = CH 2-OMe-Ph 7.27 Me Me H CH HH CCl = CH 2-OMe-Ph 7.28 Me HH CH HH CCl = CH 3-OMe-Ph 7.29 Me HH CH HH CCl = CH 4-OMe-Ph 7.42 Me HH CH HH CMe = CH Ph 7.43 Me HH CH HH CMe = CH 2-F-Ph 7.44 Me HH CH HH CMe = CH 3-F-Ph 7.45 Me HH CH HH CMe = CH 4-F-Ph 7.46 Me HH CH HH CMe = CH 2-Cl-Ph 7.47 Me HH CH HH CMe = CH 3-Cl-Ph 7.48 Me HH CH HH CMe = CH 4-Cl-Ph 7.49 Me HH CH HH CCl = CH 2-Fur 7.50 Me HH CH HH CCl = CH 3-Fur 7.51 Me HH CH HH CCl = CH 2-Thio 7.52 Me HH CH HH CCl = CH 3-Thio 7.53 Me HH CH HH CCl = CH 2-Pyr 7.54 Me HH CH HH CCl = CH 3-Pyr 7.55 Me HH CH HH CCl = CH 4- Pyr 7.56 Me HH CH HH CI = CH 2-Fur 7.57 Me HH CH HH CI = CH 3-Fur 7.58 Me HH CH HH CI = CH 2-Thio 7.59 Me HH CH HH CI = CH 3-Thio 7.60 Me HH CH HH CI = CH 2-Pyr 7.61 Me HH CH HH CI = CH 3-Pyr 7.62 Me HH CH HH CI = CH 4-Pyr 9.1 Me H 2-Me CH HH CH = CH Ph 9.2 Me H 2-Me CH HH CH = CH 2-F-Ph 9.3 Me H 2-Me CH HH CH = CH 3-F-Ph 9.4 Me H 2-Me CH HH CH = CH 4-F-Ph 9.5 Me H 2-Me CH HH CH = CH 2 , 3-F ₂ -Ph 9.6 Me H 2-Me CH HH CH = CH 2,4-F ₂ -Ph 9.7 Me H 2-Me CH HH CH = CH 2,5-F ₂ -Ph 9.8 Me H 2- Me CH HH CH = CH 2,6-F ₂ -Ph 9.9 Me H 2-Me CH HH CH = CH 3,4-F ₂ -Ph 9.10 Me H 2-Me CH HH CH = CH 3,5-F ₂ -Ph 9.11 Me H 2-Me CH HH CH = CH 2,3,5-F ₃ -Ph 9.12 Me H 2-Me CH HH CH = CH 2,4,6-F ₃ -Ph 9.13 Me H 2-Me CH HH CH = CH 2,4,5-F ₃ -Ph 9.14 Me H 2-Me CH HH CH = CH 2,3,6-F ₃ -Ph 9.15 M e H 2-Me CH HH CH = CH 2,3,5,6-F ₄ -Ph 9.16 Me H 2-Me CH HH CH = CH 2,3,4,5,6-F ₅ -Ph 9.17 Me H 2-Me CH HH CH = CH 2-Cl-Ph 9.18 Me H 2-Me CH HH CH = CH 3-Cl-Ph 9.19 Me H 2-Me CH HH CH = CH 4-Cl-Ph 9.20 Me H 2- Me CH HH CH = CH 2,3-Cl ₂ -Ph 9.21 Me H 2-Me CH HH CH = CH 2,4-Cl ₂ -Ph 9.22 Me H 2-Me CH HH CH = CH 2,5-Cl ₂ -Ph 9.23 Me H 2-Me CH HH CH = CH 2,6-Cl ₂ -Ph 9.24 Me H 2-Me CH HH CH = CH 3,4-Cl ₂ -Ph 9.25 Me H 2-Me CH HH CH = CH 3,5-Cl ₂ -Ph 9.26 Me H 2-Me CH HH CH = CH 2,3,5-Cl ₃ -Ph 9.27 Me H 2-Me CH HH CH = CH 2,4,6-Cl _3- Ph 9.28 Me H 2-Me CH HH CH = CH 2,4,5-Cl ₃ -Ph 9.29 Me H 2-Me CH HH CH = CH 2,3,6-Cl ₃ -Ph 9.30 Me H 2-Me CH HH CH = CH 2-Cl, 4-F-Ph 9.31 Me H 2-Me CH HH CH = CH 2-F, 6-Cl-Ph 9.32 Me H 2-Me CH HH CH = CH 2-Fur 9.33 Me H 2-Me CH HH CH = CH 3-Fur 9.34 Me H 2-Me CH HH CH = CH 5-Me-2-Fur 9.35 Me H 2-Me CH HH CH = CH 3-Me-2-Fur 9.36 Me H 2-Me CH HH CH = CH 5-Me-3-Fur 9.37 Me H 2-Me CH HH CH = CH 2-Me-3-Fur 9.38 Me H 2-Me CH HH CH = CH 2-Thio 9.39 Me H 2-Me CH HH CH = CH 3-Thio 9.40 Me H 2-Me CH HH CH = CH 2-Pyr 9.41 Me H 2-Me CH HH CH = CH 3-Pyr 9.42 Me H 2-Me CH HH CH = CH 4-Pyr 9.43 Me H 2-Me CH HH CH = CH 3-Me-2-Pyr 9.44 Me H 2-Me CH HH CH = CH 4-Me-2-Pyr 9.45 Me H 2-Me CH HH CH = CH 5-Me-2-Pyr 9.46 Me H 2-Me CH HH CH = CH 6-Me-2-Pyr 9.47 Me H 2-Me CH HH CH = CH 3-Pyz 9.48 Me H 2-Me CH HH CH = CH 4-Pyz 9.49 Me H 2-Me CH HH CH = CH 5-Pyz 9.50 Me H 2-Me CH HH CH = CH 2-Oxaz 9.51 Me H 2-Me CH HH CH = CH 4-Oxaz 9.52 Me H 2-Me CH HH CH = CH 5-Oxaz 9.53 Me H 2-Me CH HH CH = CH 2-Thiaz 9.54 Me H 2 -Me CH HH CH = CH 4-Thiaz 9.55 Me H 2-Me CH HH CH = CH 5-Thiaz 9.56 Me H 2-Me CH HH CH = CH 2-BFur 9.57 Me H 2-Me CH HH CH = CH 3 -BFur 9.58 Me H 2-Me CH HH CH = CH 2-BThio 9.59 Me H 2-Me CH HH CH = CH 3-BThio 9.60 Me H 2-Me CH HH CH = CH 2-BOxaz 9.61 Me H 2-Me CH HH CH = CH 2-BThiaz 中 Among the above exemplified compounds, As for 1.1,
3.1, 3.2, 3.3, 3.7, 3.8, 3.9,
3.10, 3.21, 3.22, 3.33, 3.35,
3.37, 3.45, 3.46, 4.3, 5.1, 5.
2, 5.3, 5.4, 5.5, 5.6, 5.8, 5.3
4, 5.35, 5.36, 5.47, 5.48, 5.4
9, 5.50, 5.51, 5.52, 5.60, 5.7
1, 5.75, 5.82, 5.90, 5.94, 5.9
5, 6.4, 6.45, 8.1, 8.2, 8.3, 8.
4, 8.5, 8.6, 8.8, 8.34, 8.35,
8.36, 8.47, 8.48, 8.49, 8.50,
8.51, 8.52, 8.60, 8.71, 8.75,
No. 8.82, 8.90, 8.94, 8.95.

More preferred are 1.1, 3.
2, 3.7, 3.8, 3.21, 3.35, 5.3,
5.4, 5.5, 5.6, 5.8, 5.34, 5.5
0, 5.60, 5.71, 6.4, 8.1, 8.4,
8.5, 8.6, 8.8, 8.34, 8.35, 8.3
6, 8.48, 8.49, 8.50, 8.51, 8.6
Compounds Nos. 0 and 8.71 can be mentioned.

[0036]

BEST MODE FOR CARRYING OUT THE INVENTION The aminophenol derivative of the present invention can be produced by the method described below. (Method A)

[0037]

Embedded image [During the above steps, R ¹ , R ³ , R ⁴ , R ⁵ , Z, A, Q and n
Is as defined above, L ¹ and L ² are the same or different and represent a leaving group, and R ^2a is a C1-C6 alkyl group (the alkyl group is a C1-C6 alkylthio group or a C1-C6 alkylsulfonyl group) May be substituted.),
It represents a C3-C6 alkenyl group, a C3-C6 alkynyl group or a benzyl group. The term "leaving group" in the definition of L ¹ and L ² is not particularly limited as long as it is a group which usually leaves as a nucleophilic residue, and examples thereof include halogen such as chlorine atom, bromine atom and iodine atom. C1 to C6 alkylsulfonyloxy groups such as methanesulfonyloxy; arylsulfonyloxy groups such as p-toluenesulfonyloxy; di (C1 to C6 alkylphosphonyloxy and diethylphosphinyloxy) Finyloxy group, preferably chlorine atom or methanesulfonyloxy group Step A-1 In step A-1, aminophenol (II) is converted to compound (I).
This is a step of producing an aminophenol derivative (Ia) in which R ² in the general formula (I) is a hydrogen atom among the derivatives of the present invention by etherification using II).

The reaction is performed in the presence of a base.

The base to be used is not particularly limited as long as it is a base having a strength capable of preferentially removing protons of phenols. For example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be used. Thing; sodium carbonate,
Alkali metal carbonates such as potassium carbonate; metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide; alkali metal hydrides such as sodium hydride and potassium hydride; triethylamine, tributylamine, diisopropyl Aliphatic tertiary amines such as ethylamine; 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo
[5.4.0] Aliphatic cyclic tertiary amines such as undec-7-ene (DBU); pyridines such as pyridine, collidine, and 4- (N, N-dimethylamino) pyridine;
Preferably, it is sodium hydride, potassium carbonate, sodium hydroxide or potassium hydroxide.

The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. Examples thereof include water; alcohols such as methanol, ethanol and t-butanol Ketones such as acetone and methyl isobutyl ketone; nitriles such as acetonitrile; esters such as ethyl acetate; ethers such as diethyl ether, tetrahydrofuran and dioxane; halogenations such as methylene chloride, chloroform and dichloroethane. Hydrocarbons; aromatic hydrocarbons such as toluene; amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethylsulfoxide;
Dimethylformamide or water.

The reaction temperature is usually from -70 ° C to 200 ° C, preferably from -5 ° C to 100 ° C.

The reaction time mainly depends on the reaction temperature, the starting compound,
Depending on the type of reaction reagent and solvent used,
Usually 5 minutes to 24 hours, preferably 30 minutes to 5 hours
Time. Step A-2 Step A-2 is an alkylation, alkenylation, alkynylation or benzylation of the nitrogen atom of the carbamate group of the compound (Ia) produced by the above-mentioned step A-1. )) Is a step of producing an aminophenol derivative (Ib) wherein R ² is other than a hydrogen atom.

The reaction is performed in the presence of a base.

The base to be used is not particularly limited as long as it is a base capable of releasing the proton of the carbamate group. Examples of the base include metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide. Class; alkali metal hydrides such as sodium hydride and potassium hydride; butyllithium, s-butyllithium, lithium diisopropylamide, sodium
Organometallic bases such as bistrimethylsilylamide and lithium bistrimethylsilylamide can be mentioned, preferably sodium hydride.

The reaction solvent is not particularly limited as long as it does not inhibit the reaction and dissolves the starting materials to some extent. Examples thereof include alcohols such as methanol, ethanol and t-butanol; Such ethers; amides such as dimethylformamide and dimethylacetamide; and sulfoxides such as dimethylsulfoxide, and preferably dimethylformamide.

The reaction temperature is usually from -90 ° C to 150 ° C, preferably from -50 ° C to 100 ° C.

The reaction time mainly depends on the reaction temperature, the starting compound,
Depending on the type of reaction reagent and solvent used,
Usually 5 minutes to 24 hours, preferably 15 minutes to 6 hours
Time.

The aminophenol derivative (Ia) can also be produced by the following method (Method B or Method C). (Method B)

[0049]

Embedded image [During the above steps, R ¹ , R ³ , R ⁴ , R ⁵ , Z, A, Q, L ¹
And n have the same meaning as described above, and L ³ and L ^{4 each} represent a leaving group. The term “leaving group” in the definition of L ³ and L ⁴ is not particularly limited as long as it is a group usually leaving as a nucleophilic residue, and examples thereof include halogen such as fluorine, chlorine, and bromine. Atom, preferably a fluorine atom or a chlorine atom. Step B-1 Step B-1 is a step of producing compound (VII) by reacting alcohol compound (IV) with nitro compound (V).

The reaction is performed in the presence of a base.

The base to be used is not particularly limited as long as it is a base having a strength capable of eliminating protons of alcohols. For example, metal alkoxides such as potassium t-butoxide; sodium hydride, hydride Alkali metal hydrides such as potassium; aliphatic tertiary amines such as triethylamine, tributylamine and diisopropylethylamine; 1,4-diazabicyclo [2.2.2] octane
(DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene
Aliphatic cyclic tertiary amines such as (DBU); pyridines such as pyridine, collidine, and 4- (N, N-dimethylamino) pyridine are preferable, and sodium hydride is preferable.

The solvent to be used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. Examples thereof include nitriles such as acetonitrile; Ethers; aromatic hydrocarbons such as toluene; amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethylsulfoxide; and preferably tetrahydrofuran or dimethylformamide.

The reaction temperature is usually from -70 ° C to 200 ° C, preferably from -5 ° C to 100 ° C.

The reaction time mainly depends on the reaction temperature, the starting compound,
Depending on the type of reaction reagent and solvent used,
Usually 5 minutes to 24 hours, preferably 30 minutes to 5 hours
Time. Step B-2 Step B-2 is a step of reducing the nitro compound (VII) produced in Step B-1 to reduce the aniline compound (V).
III).

This step is performed in the presence of a reducing agent.

The reducing agent used is not particularly limited as long as it reduces only a nitro group without reducing a double bond or a triple bond in the same molecule. Metal halides, sulfates of transition metals such as iron sulfate, and metals such as zinc or iron can be mentioned, preferably tin chloride or zinc.

These reducing agents are used in the presence of an acid such as hydrochloric acid and acetic acid. If necessary, the reaction is further performed in the presence of a water-miscible solvent to dissolve the nitro compound (VII).

Examples of the solvent to be used include alcohols such as methanol, ethanol and t-butanol; and ethers such as tetrahydrofuran and dioxane, preferably ethanol.

The reaction temperature is generally -50 ° C to 200 ° C, preferably 0 ° C to 100 ° C.

The reaction time mainly depends on the reaction temperature, starting compound,
Depending on the type of reaction reagent and solvent used,
Usually 5 minutes to 24 hours, preferably 30 minutes to 6 hours
Time. Step B-3 Step B-3 is a step of producing compound (Ia) from aniline compound (VIII) by carbamate-forming with compound (IX).

This step is performed in the presence of a base, if necessary.

The base used is not particularly limited as long as it is used as a base in a usual reaction. Examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; sodium carbonate, Alkali metal carbonates such as potassium carbonate; alkali metal hydrides such as sodium hydride and potassium hydride; aliphatic tertiary amines such as triethylamine, tributylamine and diisopropylethylamine; 1,4-diazabicyclo
[2.2.2] Octane (DABCO), 1,8-diazabicyclo [5.4.0]
Aliphatic cyclic tertiary amines such as undec-7-ene (DBU); pyridines such as pyridine, collidine, 4- (N, N-dimethylamino) pyridine; butyllithium, s-butyllithium, lithium diisopropyl Examples thereof include organometallic bases such as amide, sodium bistrimethylsilylamide, and lithium bistrimethylsilylamide, and are preferably triethylamine or pyridine.

The solvent to be used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. Examples thereof include water; Ketones such as acetone and methyl isobutyl ketone; nitriles such as acetonitrile; esters such as ethyl acetate; ethers such as diethyl ether, tetrahydrofuran and dioxane; halogenations such as methylene chloride, chloroform and dichloroethane. Hydrocarbons; aromatic hydrocarbons such as toluene and xylene can be mentioned, and preferred is methylene chloride.

The reaction temperature is usually from -90 ° C to 200 ° C, preferably from -50 ° C to 150 ° C.

The reaction time mainly depends on the reaction temperature, the starting compound,
Depending on the type of reaction reagent and solvent used,
Usually 5 minutes to 24 hours, preferably 15 minutes to 6 hours
Time. (Method C)

[0066]

Embedded image [During the above steps, R ¹ , R ³ , R ⁴ , R ⁵ , Z, A, Q, L ¹
And n have the same meaning as described above, and L ⁵ represents a bromine atom, an iodine atom or a trifluoromethanesulfonyl group. Step C-1 In step C-1, the phenol compound (II) is converted to the compound (I)
In this step, compound (X) is produced by etherification with X).

This step is performed in the presence of a base, and can be performed according to step A-1. Step C-2 Step C-2 is a compound (X) produced by step C-1.
Is condensed with compound (XI) to give compound (I)
This is the step of manufacturing a).

This step is performed in the presence of a catalytic amount of a transition metal compound.

Examples of the transition metal compound to be used include palladium compounds such as palladium chloride, palladium acetate, and dichlorobis (triphenylphosphine) palladium. Preferably, palladium acetate or dichlorobis (triphenylphosphine) It is palladium.

These palladium compounds are used in the presence of catalytic amounts of copper iodide, catalytic amounts of phosphorus compounds such as triphenylphosphine, and amines such as diethylamine or diisopropylamine.

Examples of the solvent used include nitriles such as acetonitrile; esters such as ethyl acetate; ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as toluene; and dimethyl sulfoxide. Sulfoxides and the like, and acetonitrile, tetrahydrofuran or dimethyl sulfoxide is preferable.

The reaction temperature is usually from 0 ° C. to 200 ° C., preferably from 20 ° C. to 100 ° C.

The reaction time mainly depends on the reaction temperature, starting compound,
Depending on the type of reaction reagent and solvent used,
Usually 5 minutes to 24 hours, preferably 30 minutes to 6 hours
Time.

The following is an example of a method for producing a compound to be used as a raw material in the above Method A, Method B or Method C.

The compound (I) which is one of the starting materials in the step A-1
I) is produced, for example, by the following method.

[0076]

Embedded image [Wherein, R ¹ , R ³ , Z and n have the same meaning as described above. The phenol compound (XIII) (this phenolic hydroxyl group may be optionally carbonated) is nitrated according to a conventional method such as a method using a mixed acid of concentrated sulfuric acid-concentrated nitric acid or a method using potassium nitrate to give phenol. To produce a 4-nitrophenol compound (XIV) in which the 4-position is nitrated. The nitro group is, for example, Pd-
4-amino which has been reduced according to a conventional method, such as a method of hydrogenation under C catalyst, a method of using stannous chloride in the presence of concentrated hydrochloric acid, or a method of using zinc chloride in acetic acid, and aminated at the 4-position of phenol A phenol compound (XV) is produced. Compound (XVI) is produced according to a conventional method using various compounds represented by the formula R ¹ OCOL ⁴ (R ¹ and L ⁴ have the same meanings as described above). This compound (X
VI) is hydrolyzed in the presence of an alkali such as sodium bicarbonate or sodium hydroxide to produce compound (II), which is a raw material of step A-1.

The other raw material (III) in Step A-1 and the compound (VI) as the raw material in Step B-1 are, for example,
It is manufactured by the following method.

[0078]

Embedded image [Wherein, R ⁴ , R ⁵ , A, Q and L ¹ have the same meanings as described above, R ⁷ represents a C1 to C4 alkyl group, and M represents a metal atom. The “metal atom” in the definition of M is not particularly limited as long as it is capable of nucleophilic attack on a carbonyl group such as an ester and a ketone together with R ⁴ or R ⁵ ,
For example, lithium atom and magnesium halide. When R ⁴ or R ⁵ is a hydrogen atom, R ⁴
Or R ⁵ and together form lithium borohydride, a reducing agent such as sodium borohydride.

The ester compound (XVII) has the formula R ⁴ M
In using a compound represented by by nucleophilic addition reaction according to a conventional method, to prepare the compound (XVIII), then to the compound (XVIII), using a compound represented by the formula R ⁵ M, normal By performing a nucleophilic addition reaction according to the method,
Compound (VI), which is a starting material for step B-1, is produced. At this time, when R ⁴ and R ⁵ represent the same substituent, two or more equivalents of the formula R ⁴ M with respect to the ester compound (XVII) are used.
Reacting the compound represented by the formula
Can be manufactured. Further, when R ⁴ and R ⁵ are both hydrogen atoms, the primary alcohol (VIa) is produced by reducing using a reducing agent such as lithium borohydride or sodium borohydride according to a conventional method. Can be.

The hydroxyl group of compound (VI) or (VIa) thus obtained is subjected to a leaving group according to a conventional method to give compound (III) or (IIIa) as a starting material in step A-2. To manufacture.

The ester compound (XVII) is, for example,
Synlett, 517, (1991), Synthesis, 498,
(1987).

After completion of each of the above reaction steps, the target compound of each step can be collected from the reaction mixture according to a conventional method. For example, it can be obtained by appropriately neutralizing the reaction mixture, removing any insoluble matter by filtration, adding an organic solvent immiscible with water, washing with water, and distilling off the solvent. If necessary, the obtained target compound can be further purified by a conventional method, for example, recrystallization, reprecipitation or chromatography.

The compound of the present invention may be mixed with a carrier and, if necessary, other adjuvants to prepare a preparation usually used as a herbicide, for example, powder, coarse powder, granule, granule, wettable powder, It is prepared and used in aqueous solvents, emulsions, solutions and the like. A carrier as used herein refers to a synthetic or natural inorganic or organic substance that is mixed into a herbicide to help the active ingredient compound reach plants or to facilitate storage, transportation or handling of the active ingredient. means.

Suitable solid carriers include, for example, clays represented by kaolinite group, montmorillonite group, attapulgite group, talc, mica, pyrophyllite, pumice, vermiculite, gypsum, dolomite, diatomaceous earth, magnesium Lime, phosphorous lime, zeolite, silicic anhydride, synthetic calcium silicate, kaolin, bentonite,
Inorganic substances such as calcium carbonate, soybean flour, tobacco flour, walnut flour, flour, wood flour, starch, vegetable organic substances such as crystalline cellulose, coumarone resin, petroleum resin, alkyd resin, polyvinyl chloride, polyalkylene glycol, ketone Synthetic or natural polymer compounds such as resin, ester gum, copal gum, dammar gum, etc .; waxes such as carnauba wax, paraffin wax and beeswax; urea;

Suitable liquid carriers include, for example, paraffinic or naphthenic hydrocarbons such as kerosene, mineral oil, spindle oil and white oil; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene and methylnaphthalene; Carbon tetrachloride, chloroform,
Chlorinated hydrocarbons such as trichloroethylene, monochlorobenzene, chlorotoluene, ethers such as dioxane and tetrahydrofuran, acetone, methyl ethyl ketone,
Ketones such as diisobutyl ketone, cyclohexanone, acetophenone, and isophorone; esters such as ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate, dibutyl maleate, and diethyl succinate; methanol, hexanol, ethylene glycol, diethylene glycol, cyclohexanol, Examples thereof include alcohols such as benzyl alcohol, ether alcohols such as ethylene glycol ethyl ether, ethylene glycol phenyl ether, diethylene glycol ethyl ether, and diethylene glycol butyl ether; polar solvents such as dimethylformamide and dimethyl sulfoxide; and water.

Surfactants used for the purpose of emulsification, dispersion, wetting, spreading, binding, control of disintegration, stabilization of active ingredients, improvement of fluidity, rust prevention, promotion of absorption into plants, etc. may be ionic. It may be non-ionic.

Suitable nonionic surfactants include, for example, sucrose esters of fatty acids, ethylene oxide oxide adducts of higher aliphatic alcohols such as lauryl alcohol, stearyl alcohol and oleyl alcohol, and alkylphenols such as isooctylphenol and nonylphenol. Polymerized adducts of ethylene oxide, ethylene oxide adducts of alkyl naphthols such as butyl naphthol and octyl naphthol, ethylene oxide polymer adducts of higher fatty acids such as palmitic acid, stearic acid, and oleic acid; Polymerized ethylene oxide adducts of phosphoric acid, ethylene oxide adducts of higher aliphatic amines such as dodecylamine and stearamide, higher fatty acid esters of polyhydric alcohols such as sorbitan, and their oxidized oxides Copolymers of emissions polymerization adducts and ethylene oxide and propylene oxide can be cited.

Suitable anionic surfactants include, for example, alkyl sulfates such as sodium lauryl sulfate and amine salt of oleyl alcohol sulfate, and fatty acid salts such as sodium dioctyl ester sulfosuccinate, sodium oleate and sodium stearate. ,
Examples thereof include alkylaryl sulfonates such as sodium isopropylnaphthalenesulfonate, sodium methylenebisnaphthalenesulfonate, sodium ligninsulfonate, and sodium dodecylbenzenesulfonate.

Suitable cationic surfactants include, for example, higher aliphatic amines, quaternary ammonium salts, alkylpyridinium salts and the like.

The herbicide of the present invention may further contain other components such as gelatin, gum arabic, casein, albumin, glue, sodium alginate, polyvinyl alcohol, and the like, for the purpose of improving the properties of the preparation and enhancing the biological effect. Carboxymethylcellulose, methylcellulose,
It may contain a high molecular compound such as hydroxymethylcellulose, a thixotropic agent such as sodium polyphosphate and bentonite, and other auxiliary agents.

The above carriers and various auxiliaries are used singly or in combination depending on the purpose, depending on the application of the formulation.

Powders usually contain 2 to 10 parts by weight of the active ingredient compound, and the balance is a solid carrier. The wettable powder usually contains 10 to 80 parts by weight of the active ingredient, and the remainder is a solid carrier and a dispersing wetting agent. If necessary, a protective colloid agent, a thixotropic agent, an antifoaming agent and the like are added.

The granules usually contain 0.1 to 10 parts by weight of the active ingredient compound, and the remainder is mostly a solid carrier. The active ingredient compound is uniformly mixed with the solid carrier or is uniformly fixed or adsorbed on the surface of the solid carrier, and the particle diameter is about 0.2 to 1.5 mm.

The emulsion usually contains 1 to 50 parts by weight of the active ingredient, and contains about 5 to 20 parts by weight of the emulsion, the remainder being a liquid carrier, and if necessary, a rust inhibitor is added. .

When the compound of the present invention thus prepared in various dosage forms is subjected to soil treatment before or after germination of a weed in a paddy field, for example, 1 to 1000 g, preferably 10 to 1000 g, as an active ingredient per 10a is used. By treating 300 g, weeds can be effectively controlled.

It is preferable that other herbicides are added to the herbicide of the present invention in order to broaden the herbicidal spectrum. In some cases, a synergistic effect can be expected.

The herbicide of the present invention can of course be used in admixture with other plant growth regulators, fungicides, insecticides, acaricides, nematicides or fertilizers.

[0098] Examples of the herbicide of the present invention, formulation examples and test examples will be shown below to specifically explain, but the present invention is not limited to these.

[0099]

【Example】

[0100]

Example 1 Methyl N- {2-methyl-4- (3-phenylpro-2-pinyloxy) phenyl} carbamate (Compound No. 3.2) (1) Methyl N- (4-hydroxy-2-methylphenyl) ) Carbamate 12.6 g of 4-amino-3-methylphenol were dissolved in 100 ml of acetone, and 10.1 g of sodium bicarbonate and 8.1 m of methyl chloroformate were added to this solution in an ice water bath.
1 was added in sequence, and the mixture was heated to room temperature and stirred for 1 hour. After completion of the reaction, insolubles of the reaction mixture were removed by filtration, the solvent of the filtrate was distilled off under reduced pressure, and the obtained residue was subjected to silica gel chromatography (elution solvent: hexane / ethyl acetate = 5/5).
5) to give 17.2 g of the title compound (yield 95).
%). Physical properties: amorphous ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.22 (1H,
br.s), 6.61-6.52 (2H, m), 6.26 (2H, br.s), 3.76 (3
H, s), 2.17 (3H, s). (2) Methyl N- {2-methyl-4- (3-phenylpro-2-pinyloxy) phenyl} carbamate (Compound No. 3.2) (Step A-1) ) 108.5 m of methyl N- (4-hydroxy-2-methylphenyl) carbamate produced by the method of (1) above
g was dissolved in 1 ml of dimethylformamide and 26.3 m of sodium hydride (60%) were added to this solution in an ice-water bath.
g, and the mixture was stirred at the same temperature for 10 minutes. Then, 18.2 ml of 18.2% of 1-phenyl-3-chloro-1-propyne in 1 ml of dimethylformamide was added to the reaction solution at the same temperature, and the mixture was stirred at the same temperature for 1 hour. After the temperature was raised to room temperature, the mixture was further stirred at room temperature for 2 hours. After completion of the reaction, a saturated aqueous solution of ammonium chloride was added to the reaction solution, extracted with ethyl acetate, washed with water and saturated saline, and dried over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel chromatography (eluent: hexane / ethyl acetate = 6/1 to 4/1) to give 78.6 mg of the title compound (yield). 44%). Melting point: 112-113 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.59-7.40
(3H, m), 7.36-7.24 (3H, m), 6.92-6.84 (2H, m), 6.
21 (1H, br.s), 4.88 (2H, s), 3.77 (3H, s), 2.25 (3
H, s).

[0101]

Example 2 Methyl N- {2- (3-phenylpro-
2-Pinyloxy) pyridin-5-yl} carbamate (Compound No. 3.35) (1) 5-Nitro-2- (3-phenylpro-2-pinyloxy) pyridine (Step B-1) 3-Phenylpro-2 1.67 g of pin-1-ol are dissolved in 20 ml of tetrahydrofuran, and 0.48 g of sodium hydride (60%) and 2
1.60 g of -chloro-5-nitropyridine were added sequentially,
Stir at room temperature for 3 hours. After completion of the reaction, a saturated saline solution was added to the reaction solution, extracted with ethyl acetate, and washed with a saturated saline solution.
Dry over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel chromatography (elution solvent: hexane / ethyl acetate = 9/1) to obtain 2.21 g (yield 87%) of the title compound. Obtained. Melting point: 122-123 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 9.12 (1H,
d, J = 3.0Hz), 8.40 (1H, dd, J = 9.1, 3.0Hz), 7.49-7.
44 (2H, m), 7.36-7.31 (3H, m), 6.93 (1H, d, J = 9.1H
z), 5.31 (2H, s). (2) 5-Amino-2- (3-phenylpro-2-pinyloxy) pyridine (Step B-2) 5-Nitro-2 produced by the method of (1) above. 512 mg of-(3-phenylpro-2-pinyloxy) pyridine was dissolved in 10 ml of acetic acid, and 1.46 g of zinc powder (90%) was added to this solution in an ice water bath, followed by stirring at room temperature for 1 hour. After the completion of the reaction, water was added to the reaction solution, neutralized with an aqueous sodium hydrogen carbonate solution, extracted with ethyl acetate, washed with saturated saline, and dried over anhydrous sodium sulfate. After filtration of the drying agent, the solvent was distilled off under reduced pressure to obtain 653 mg of the title compound. This compound was subjected to the next reaction without purification. (3) Methyl N- {2- (3-phenylpro-2-)
(Pinyloxy) pyridin-5-yl} carbamate (Compound No. 3.35) (Step B-3) 653 mg of 5-amino-2- (3-phenylpro-2-pinyloxy) pyridine produced by the method of the above (2) was obtained. Dissolve in 10 ml of acetone and add 253 mg of sodium bicarbonate and 0.1 ml of methyl chloroformate in an ice-water bath.
17 ml was sequentially added, and the mixture was heated to room temperature and stirred for 1 hour. After completion of the reaction, a saturated saline solution was added to the reaction solution, extracted with ethyl acetate, washed with a saturated saline solution, and dried over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off under reduced pressure, and the obtained residue was subjected to silica gel chromatography (elution solvent:
The residue was purified by hexane / ethyl acetate = 7/3) to obtain 485 mg (yield: 85%) of the title compound. Melting point: 119-120 ° C ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 8.10 (1H,
d, J = 2.6Hz), 7.83-7.78 (1H, m), 7.49-7.43 (2H, m),
7.32-7.29 (3H, m), 6.83 (2H, d, J = 8.8Hz), 6.47 (1
H, br.s), 5.17 (2H, s), 3.78 (3H, s).

[0102]

Example 3 Methyl N- [4- {3- (benzofura-
2-Nyl) pro-2-pinyloxy} -2-methylphenyl] carbamate (Compound No. 8.90) (1) Methyl N- {2-methyl-4- (pro-2-
Pinyloxy) phenyl} carbamate (Step C-1) Methyl N- (4- produced by the method of Example 1- (1)
(Hydroxy-2-methylphenyl) carbamate 5.4
4 g was dissolved in 60 ml of acetone, and 4.98 g of potassium carbonate and 2.7 m of propargyl bromide were added to this solution.
1 were added in sequence, and the mixture was refluxed for 5 hours. After completion of the reaction, a saturated saline solution was added to the reaction solution, extracted with ethyl acetate, washed with a saturated saline solution, and dried over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off under reduced pressure, and the obtained residue was subjected to silica gel chromatography (elution solvent: hexane / ethyl acetate = 7).
/ 3) to give 6.27 g of the title compound (yield 95).
%). Melting point: 80-81 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.55-7.48
(1H, m), 6.85-6.80 (2H, m), 6.20 (1H, br.s), 4.66
(2H, d, J = 2.4Hz), 3.76 (3H, s), 2.51 (1H, t, J = 2.
4Hz), 2.24 (3H, s). (2) Methyl N- [4- {3- (benzofura-2-
Nyl) pro-2-pinyloxy {-2-methylphenyl] carbamate (Compound No. 8.90) (Step C-2) Methyl N- {2-methyl-4- (pro- 222 mg of 2-pinyloxy) phenyl dicarbamate and 272 mg of 2-iodobenzofuran
Was dissolved in 5 ml of acetonitrile, and 13 mg of triphenylphosphine, 0.16 ml of diisopropylamine, 4 mg of copper iodide and 14 mg of dichlorobis (triphenylphosphine) palladium were sequentially added to this solution,
Refluxed for 4 hours. After completion of the reaction, a saturated saline solution was added to the reaction solution, extracted with ethyl acetate, washed with a saturated saline solution, and dried over anhydrous sodium sulfate. After filtering the drying agent, the solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel chromatography (elution solvent: hexane / ethyl acetate = 7/3) to obtain 257 mg (yield: 76%) of the title compound. . Melting point: 133-134 ° C ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.56-7.19
(5H, m), 6.96 (1H, s), 6.90-6.85 (2H, m), 6.24 (1
H, br.s), 4.93 (2H, s), 3.76 (3H, s), 2.24 (3H,
s). ¹ H-NMR data and physical properties (melting point) of the compounds synthesized in the same manner as in Examples 1 to 3 are shown below.

[0103]

Example 4 Methyl N- {4- (3-phenylpro-
2-Pinyloxy) phenyl dicarbamate (Compound No. 1.1) Melting point: 93-94 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.48-7.40
(2H, m), 7.38-7.24 (5H, m), 6.99 (2H, d, J = 9.1H
z), 6.48 (1H, br, s), 4.89 (2H, s), 3.77 (3H, s).

[0104]

Example 5 Methyl N- {3-methyl-4- (3-phenylpro-2-pinyloxy) phenyl} carbamate (Compound No. 3.1) Physical properties: Oil ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.46-7.41
(2H, m), 7.34-7.29 (3H, m), 7.19-7.16 (2H, m), 7.
69 (1H, d, J = 8.3Hz), 6.43 (1H, br.s), 4.89 (2H,
s), 3.76 (3H, s), 2.25 (3H, s).

[0105]

Example 6 Methyl N- {2,3-dimethyl-4-
(3-phenylpro-2-pinyloxy) phenyl} carbamate (Compound No. 3.3) Melting point: 134-136 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.46-7.40
(2H, m), 7.33-7.29 (4H, m), 6.93 (1H, d, J = 8.9H
z), 6.20 (1H, br.s), 4.90 (2H, s), 3.76 (3H, s),
2.23 (3H, s), 2.18 (3H, s).

[0106]

Example 7: Methyl N- {2-methoxy-4- (3-
Phenylpro-2-pinyloxy) phenyl dicarbamate (Compound No. 3.21) Melting point: 73-74 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.97-7.93
(1H, m), 7.46-7.40 (2H, m), 7.34-7.29 (3H, m), 7.
00 (1H, br.s), 6.66-6.60 (2H, m), 4.89 (2H, s), 3.8
4 (3H, s), 3.77 (3H, s).

[0107]

Example 8 Methyl N- {3-methoxy-4- (3-
Phenylpro-2-pinyloxy) phenyl} carbamate (Compound No. 3.22) Melting point: 98-101 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.44-7.39
(2H, m), 7.33-7.23 (4H, m), 7.05 (1H, d, J = 8.6H
z), 6.74 (1H, dd, J = 8.6, 2.5Hz), 6.52 (1H, br.s),
4.94 (2H, s), 3.89 (3H, s), 3.77 (3H, s).

[0108]

Example 9 Methyl N- {2-fluoro-4- (3-
Phenylpro-2-pinyloxy) phenyl dicarbamate (Compound No. 3.7) Melting point: 83-84 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.95-7.85
(1H, m), 7.46-7.42 (2H, m), 7.35-7.28 (3H, m), 6.
85-6.77 (2H, m), 6.61 (1H, br.s), 4.88 (2H, s), 3.7
9 (3H, s).

[0109]

Example 10 Methyl N- {2-chloro-4- (3-
Phenylpro-2-pinyloxy) phenyl dicarbamate (Compound No. 3.8) Melting point: 64-66 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 8.02 (1H,
d, J = 8.9Hz), 7.47-7.39 (2H, m), 7.34-7.28 (3H,
m), 7.07 (1H, d, J = 2.8Hz), 6.97 (1H, dd, J = 8.9, 2.
8Hz), 6.91 (1H, br.s), 4.88 (2H, s), 3.74 (3H, s).

[0110]

Example 11 Methyl N- {3-fluoro-4- (3
-Phenylpro-2-pinyloxy) phenyl} carbamate (Compound No. 3.9) Melting point: 98-101 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.44-7.27
(6H, m), 7.13 (1H, t, J = 8.8Hz), 7.00-6.98 (1H, m),
6.52 (1H, br.s), 4.95 (2H, s), 3.78 (3H, s).

[0111]

Example 12 Methyl N- {3-chloro-4- (3-
Phenylpro-2-pinyloxy) phenyl dicarbamate (Compound No. 3.10) Melting point: 110 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.49-7.39
(3H, m), 7.34-7.21 (4H, m), 7.23 (1H, d, J = 8.9H
z), 6.51 (1H, br.s), 4.97 (2H, s), 3.77 (3H, s).

[0112]

Example 13 Methyl N- {5-chloro-2-methyl-4- (3-phenylpro-2-pinyloxy) phenyl} carbamate (Compound No. 3.33) Melting point: 105-107 ° C ¹ H-NMR spectrum (200MHz, CDCl ₃ ) δ (ppm): 7.75 (1H,
br.s), 7.46-7.39 (2H, m), 7.35-7.27 (3H, m), 6.99
(1H, s), 6.22 (1H, br.s), 4.96 (2H, s), 3.78 (3H,
s), 2.25 (3H, s).

[0113]

Example 14 Methyl N- {3-methyl-2- (3-
Phenylpro-2-pinyloxy) pyridin-5-yl
Carbamate (Compound No. 3.37) Melting point: 107-108 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.92 (1H,
d, J = 2.6Hz), 7.64 (1H, br.s), 7.49-7.43 (2H, m),
7.33-7.28 (3H, m), 6.43 (1H, br.s), 5.18 (2H, s),
3.78 (3H, s), 2.25 (3H, s).

[0114]

Example 15 Methyl N- {4- (3-phenylpro-2-pinyloxy) -1-naphthyl} carbamate (Compound No. 3.46) Melting point: 169-171 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃₎ ) δ (ppm): 8.39-8.34
(1H, m), 7.88-7.84 (1H, m), 7.61-7.41 (5H, m), 7.
33-7.29 (3H, m), 7.03 (1H, d, J = 8.4Hz), 6.55 (1H, b
rs), 5.12 (2H, s), 3.81 (3H, s).

[0115]

Example 16 Methyl N- {8- (3-phenylpro-2-pinyloxy) -5-quinolyl} carbamate (Compound No. 3.47) Melting point: 172 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 8.98 (1H,
dd, J = 4.2, 1.7Hz), 8.25 (1H, dd, J = 8.6, 1.7Hz),
7.65-7.60 (1H, m), 7.48-7.27 (7H, m), 6.64 (1H, b
rs), 5.24 (2H, s), 3.81 (3H, s).

[0116]

Example 17 Methyl N- {4- (1,1-dimethyl-3-phenylpro-2-pinyloxy) phenyl} carbamate (Compound No. 4.3) Physical properties: Oil ¹ H-NMR spectrum (200 MHz, CDCl ₃₎ ) δ (ppm): 7.41-7.18
(9H, m), 6.54 (1H, br.s), 3.76 (3H, s), 1.69 (6H,
s).

[0117]

Example 18 Methyl N- [4- {3- (2-methylphenyl) pro-2-pinyloxy} phenyl] carbamate (Compound No. 5.1) Melting point: 79-80 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.39 (1H,
d, J = 7.0Hz), 7.31 (2H, d, J = 9.0Hz), 7.23-7.10 (3
H, m), 7.00 (2H, d, J = 9.0Hz), 6.45 (1H, br.s), 4.9
4 (2H, s), 3.76 (3H, s), 2.37 (3H, s).

[0118]

Example 19 Methyl N- [4- {3- (4-methylphenyl) pro-2-pinyloxy} phenyl] carbamate (Compound No. 5.2) Physical properties: Oil ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.31 (2H,
d, J = 8.9Hz), 7.25-7.13 (4H, m), 7.31 (2H, d, J = 8.
9Hz), 6.49 (1H, br.s), 4.87 (2H, s), 3.76 (3H, s),
2.31 (3H, s).

[0119]

Example 20 Methyl N- [4- {3- (4-methylphenyl) pro-2-pinyloxy} phenyl] carbamate (Compound No. 5.3) Melting point: 119-122 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.33 (2H,
d, J = 7.7Hz), 7.31 (2H, d, J = 9.0Hz), 7.11 (2H, d,
J = 7.7Hz), 6.99 (2H, d, J = 9.0Hz), 6.47 (1H, br.s),
4.88 (2H, s), 3.77 (3H, s), 2.34 (3H, s).

[0120]

Example 21 Methyl N- [4- {3- (2-fluorophenyl) pro-2-pinyloxy} phenyl] carbamate (Compound No. 5.4) Melting point: 90-92 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.46-7.33
(2H, m), 7.31 (2H, d, J = 8.1Hz), 7.12-7.04 (2H, m),
7.00 (2H, d, J = 8.1Hz), 6.48 (1H, br.s), 4.92 (2H,
s), 3.76 (3H, s).

[0121]

Example 22 Methyl N- [4- {3- (3-fluorophenyl) pro-2-pinyloxy} phenyl] carbamate (Compound No. 5.5) Melting point: 93-94 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.32 (2H,
d, J = 9.4Hz), 7.22-7.02 (4H, m), 6.98 (2H, d, J = 9.
4Hz), 6.49 (1H, br.s), 4.88 (2H, s), 3.77 (3H, s).

[0122]

Example 23 Methyl N- [4- {3- (4-fluorophenyl) pro-2-pinyloxy} phenyl] carbamate (Compound No.5.6) Melting point: 139-142 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.48-7.25
(4H, m), 7.05-6.90 (4H, m), 6.47 (1H, br.s), 4.87
(2H, s), 3.77 (3H, s).

[0123]

Example 24 Methyl N- [4- {3- (2,4-difluorophenyl) pro-2-pinyloxy} phenyl] carbamate (Compound No. 5.8) Melting point: 99-103 ° C. ¹ H-NMR spectrum ( 200MHz, CDCl ₃ ) δ (ppm): 7.43-7.38
(1H, m), 7.31 (2H, d, J = 9.0Hz), 6.99 (2H, d, J = 9.0
Hz), 6.87-6.78 (2H, m), 6.47 (1H, br.s), 4.90 (2H,
s), 3.77 (3H, s).

[0124]

Example 25 Methyl N- [4- {3- (2-methoxyphenyl) pro-2-pinyloxy} phenyl] carbamate (Compound No. 5.34) Property: Oil ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.40-7.28
(4H, m), 7.02 (2H, d, J = 9.0Hz), 6.92-6.84 (2H, m),
6.45 (1H, br.s), 4.93 (2H, s), 3.87 (3H, s), 3.77
(3H, s).

[0125]

Example 26 Methyl N- [4- {3- (3-methoxyphenyl) pro-2-pinyloxy} phenyl] carbamate (Compound No. 5.35) Melting point: 93-96 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.31 (2H,
d, J = 9.1Hz), 7.20 (1H, d, J = 8.0Hz), 7.05-6.96 (2
H, m), 6.99 (2H, d, J = 9.1Hz), 6.91-6.85 (1H, m), 6.
47 (1H, br.s), 4.88 (2H, s), 3.79 (3H, s), 3.77 (3
H, s).

[0126]

Example 27 Methyl N- [4- {3- (4-methoxyphenyl) pro-2-pinyloxy} phenyl] carbamate (Compound No. 5.36) Melting point: 128-130 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.38 (2H,
d, J = 9.0Hz), 7.31 (2H, d, J = 9.1Hz), 6.98 (2H, d,
J = 9.1Hz), 6.83 (2H, d, J = 9.0Hz), 6.47 (1H, br.s),
4.87 (2H, s), 3.81 (3H, s), 3.76 (3H, s).

[0127]

Example 28 Methyl N- [4- {3- (2-trifluoromethylphenyl) pro-2-pinyloxy} phenyl] carbamate (Compound No. 5.47) Physical properties: Oil ¹ H-NMR spectrum (200 MHz, CDCl 2) ₃ ) δ (ppm): 7.65-7.41
(4H, m), 7.31 (2H, d, J = 8.9Hz), 7.00 (2H, d, J = 8.9Hz)
Hz), 6.47 (1H, br.s), 4.92 (2H, s), 3.76 (3H, s).

[0128]

Example 29 Methyl N- [4- {3- (3-trifluoromethylphenyl) pro-2-pinyloxy} phenyl] carbamate (Compound No. 5.48) Melting point: 102-103 ° C. ¹ H-NMR spectrum ( 200MHz, CDCl ₃ ) δ (ppm): 7.69 (1H,
br.s), 7.62-7.55 (2H, m), 7.47-7.39 (1H, m), 7.32
(2H, d, J = 9.1Hz), 6.98 (2H, d, J = 9.1Hz), 6.48 (1H,
br.s), 4.89 (2H, s), 3.77 (3H, s).

[0129]

Example 30 Methyl N- [4- {3- (4-trifluoromethylphenyl) pro-2-pinyloxy} phenyl] carbamate (Compound No. 5.49) Melting point: 140-143 ° C. ¹ H-NMR spectrum ( 200MHz, CDCl ₃ ) δ (ppm): 7.59-7.50
(4H, m), 7.32 (2H, d, J = 9.0Hz), 6.98 (2H, d, J = 9.0
Hz), 6.48 (1H, br.s), 4.90 (2H, s), 3.77 (3H, s).

[0130]

Example 31 Methyl N- [4- {3- (2-furyl) pro-2-pinyloxy} phenyl] carbamate (Compound No. 5.50) Melting point: 102-103 ° C. ¹ H-NMR spectrum (200 MHz, CDCl 2) ₃ ) δ (ppm): 7.37 (1H,
d, J = 1.9Hz), 7.31 (2H, d, J = 8.8Hz), 6.96 (2H, d,
J = 8.8Hz), 6.61 (1H, d, J = 3.6Hz), 6.49 (1H, br.s),
6.38 (1H, dd, J = 3.6, 1.9Hz), 4.89 (2H, s), 3.77 (3
H, s).

[0131]

Example 32 Methyl N- [4- {3- (3-furyl) pro-2-pinyloxy} phenyl] carbamate (Compound No. 5.51) Melting point: 90-92 ° C. ¹ H-NMR spectrum (200 MHz, CDCl 2) ₃ ) δ (ppm): 7.61 (1H,
s), 7.35 (1H, t, J = 1.8Hz), 7.30 (2H, d, J = 9.0Hz),
7.00-6.92 (2H, m), 6.49 (1H, br.s), 6.43 (1H, d,
J = 1.8Hz), 4.84 (2H, s), 3.76 (3H, s).

[0132]

Example 33 Methyl N- [4- {3- (5-methyl-2-furyl) pro-2-pinyloxy} phenyl] carbamate (Compound No. 5.52) Melting point: 92-94 ° C. ¹ H-NMR spectrum (200MHz, CDCl ₃ ) δ (ppm): 7.30 (2H,
d, J = 9.1Hz), 7.00-6.94 (2H, m), 6.51 (1H, d, J = 3.
3Hz), 6.47 (1H, br.s), 5.95 (1H, d, J = 3.3Hz), 4.89
(2H, s), 3.76 (3H, s), 2.29 (3H, s).

[0133]

Example 34 Methyl N- [4- {3- (2-thienyl) pro-2-pinyloxy} phenyl] carbamate (Compound No. 5.60) Melting point: 88-90 ° C. ¹ H-NMR spectrum (200 MHz, CDCl 2) ₃ ) δ (ppm): 7.33-7.21
(4H, m), 7.01-6.93 (3H, m), 6.48 (1H, br.s), 4.89
(2H, s), 3.76 (3H, s).

[0134]

Example 35 Methyl N- [4- {3- (3-pyridyl) pro-2-pinyloxy} phenyl] carbamate (Compound No. 5.71) Melting point: 163-166 ° C. ¹ H-NMR spectrum (200 MHz, CDCl 2) ₃ ) δ (ppm): 8.67 (1H,
d, J = 2.1Hz), 8.55 (1H, dd, J = 4.9, 1.6Hz), 7.72
(1H, td, J = 7.9, 2.1Hz), 7.32 (2H, d, J = 8.9Hz), 7.2
8-7.21 (1H, m), 6.98 (2H, d, J = 8.9Hz), 6.53 (1H, b
rs), 4.90 (2H, s), 3.77 (3H, s).

[0135]

Example 36 Methyl N- [4- {3- (5-methyl-2-pyridyl) pro-2-pinyloxy} phenyl]
Carbamate (Compound No. 5.75) Melting point: 128-130 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 8.39 (1H,
d, J = 1.5Hz), 7.44 (1H, dd, J = 7.8, 1.5Hz), 7.34-7.
28 (3H, m), 7.02-6.90 (2H, m), 6.64 (1H, br.s), 4.
89 (2H, s), 3.76 (3H, s), 2.34 (3H, s).

[0136]

Working Example 37 Methyl N- [2-methyl-4- {3-}
(1H-Pyraz-4-yl) pro-2-pinyloxy}
Phenyl] carbamate (Compound No. 5.82) Melting point: 141-142 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.70 (2H,
s), 7.56-7.50 (1H, m), 6.90-6.84 (2H, m), 6.23 (1
H, br.s), 4.85 (2H, s), 3.77 (3H, s), 2.24 (3H,
s).

[0137]

Example 38 Methyl N- [4- {3- (benzofuran-2-yl) pro-2-pinyloxy} phenyl] carbamate (Compound No. 5.90) Melting point: 125-126 ° C. ¹ H-NMR spectrum (200 MHz) , CDCl ₃ ) δ (ppm): 7.54 (1H,
d, J = 7.6Hz), 7.44 (1H, d, J = 7.6Hz), 7.37-7.18 (4
H, m), 7.01-6.95 (3H, m), 6.62 (1H, br.s), 4.92 (2
H, s), 3.75 (3H, s).

[0138]

Example 39: Methyl N- [4- {3- (benzoxazo-2-yl) pro-2-pinyloxy} phenyl]
Carbamate (Compound No. 5.94) Melting point: 140-143 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.77-7.72
(1H, m), 7.55-7.31 (5H, m), 7.03-6.97 (2H, m), 6.
49 (1H, br.s), 4.96 (2H, s), 3.77 (3H, s).

[0139]

Example 40 Methyl N- [4- {3- (benzothiazo-2-yl) pro-2-pinyloxy} phenyl] carbamate (Compound No. 5.95) Melting point: 151-152 ° C. ¹ H-NMR spectrum (200 MHz) , CDCl ₃ ) δ (ppm): 8.06 (1H,
d, J = 7.6Hz), 7.85 (1H, d, J = 7.6Hz), 7.56-7.41 (2
H, m), 7.33 (2H, d, J = 8.8Hz), 6.99 (2H, d, J = 8.8H
z), 6.60 (1H, br.s), 4.96 (2H, s), 3.76 (3H, s).

[0140]

Working Example 41 Methyl N- [2-methyl-4- {3-
(2-Methylphenyl) pro-2-pinyloxydiphenyl] carbamate (Compound No. 8.1) Melting point: 74-75 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.54 (1H,
br.s), 7.39 (1H, d, J = 7.0Hz), 7.23-7.05 (3H, m),
6.92-6.89 (2H, m), 6.19 (1H, br.s), 4.93 (2H, s),
3.76 (3H, s), 2.38 (3H, s), 2.24 (3H, s).

[0141]

Example 42 Methyl N- [2-methyl-4- {3-
(3-Methylphenyl) pro-2-pinyloxydiphenyl] carbamate (Compound No. 8.2) Melting point: 107-120 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.53-7.49
(2H, m), 7.22-7.13 (3H, m), 6.90-6.85 (2H, m), 6.
19 (1H, br.s), 4.86 (2H, s), 3.76 (3H, s), 2.31 (3
H, s), 2.24 (3H, s).

[0142]

Example 43 Methyl N- [2-methyl-4- {3-
(4-Methylphenyl) pro-2-pinyloxydiphenyl] carbamate (Compound No. 8.3) Melting point: 95-98 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.52 (1H,
br.s), 7.33 (2H, d, J = 8.1Hz), 7.11 (2H, d, J = 8.1H
z), 6.91-6.85 (2H, m), 6.20 (1H, br.s), 4.87 (2H,
s), 3.77 (3H, s), 2.34 (3H, s), 2.24 (3H, s).

[0143]

Working Example 44 Methyl N- [4- {3- (2-fluorophenyl) pro-2-pinyloxy} -2-methylphenyl] carbamate (Compound No. 8.4) Melting Point: 115-117 ° C. ¹ H-NMR Spectrum (200MHz, CDCl ₃ ) δ (ppm): 7.47-7.28
(3H, m), 7.12-7.01 (2H, m), 6.91-6.86 (2H, m), 6.
21 (1H, br.s), 5.30 (2H, s), 3.76 (3H, s), 2.24 (3
H, s).

[0144]

Example 45 Methyl N- [4- {3- (3-fluorophenyl) pro-2-pinyloxy} -2-methylphenyl] carbamate (Compound No. 8.5) Melting point: 98-100 ° C. ¹ H-NMR Spectrum (200MHz, CDCl ₃ ) δ (ppm): 7.51 (1H,
br.s), 7.50-6.98 (4H, m), 6.98-6.85 (2H, m), 6.24
(1H, br.s), 4.87 (2H, s), 3.76 (3H, s), 2.25 (3H,
s).

[0145]

Example 46 Methyl N- [4- {3- (4-fluorophenyl) pro-2-pinyloxy} -2-methylphenyl] carbamate (Compound No. 8.6) Melting point: 109-110 ° C. ¹ H-NMR Spectrum (200MHz, CDCl ₃ ) δ (ppm): 7.80 (1H,
d, J = 8.0Hz), 7.69-7.64 (1H, m), 7.52-7.47 (1H,
m), 7.37-7.26 (4H, m), 6.20 (1H, br, s), 4.86 (2H,
s), 3.78 (3H, s), 2.25 (3H, s).

[0146]

Example 47 Methyl N- [4- {3- (2,4-difluorophenyl) pro-2-pinyloxy} -2-methylphenyl] carbamate (Compound No. 8.8) Melting point: 121-123 ° C. ¹ H -NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.55-7.35
(2H, m), 6.91-6.78 (4H, m), 6.19 (1H, br.s), 4.89
(2H, s), 3.77 (3H, s), 2.25 (3H, s).

[0147]

Example 48 Methyl N- [4- {3- (2-methoxyphenyl) pro-2-pinyloxy} -2-methylphenyl] carbamate (Compound No. 8.34) Physical properties: Oil ¹ H-NMR spectrum (200 MHz) , CDCl ₃ ) δ (ppm): 7.54 (1H,
br.s), 7.41-7.28 (2H, m), 6.94-6.84 (4H, m), 6.20
(1H, br.s), 4.92 (2H, s), 3.87 (3H, s), 3.77 (3H,
s), 2.24 (3H, s).

[0148]

Example 49 Methyl N- [4- {3- (3-methoxyphenyl) pro-2-pinyloxy} -2-methylphenyl] carbamate (Compound No. 8.35) Melting point: 68-70 ° C. ¹ H-NMR Spectrum (200MHz, CDCl ₃ ) δ (ppm): 7.52 (1H,
br.s), 7.20 (1H, d, J = 7.9Hz), 7.05-6.86 (5H, m),
6.21 (1H, br.s), 4.88 (2H, s), 3.76 (3H, s), 3.72
(3H, s), 2.24 (3H, s).

[0149]

Example 50 Methyl N- [4- {3- (4-methoxyphenyl) pro-2-pinyloxy} -2-methylphenyl] carbamate (Compound No. 8.36) Melting point: 106-109 ° C. ¹ H-NMR Spectrum (200MHz, CDCl ₃ ) δ (ppm): 7.41 (1H,
br.s), 7.38 (2H, d, J = 9.0Hz), 6.91-6.79 (2H, m),
6.83 (2H, d, J = 9.0Hz), 6.20 (1H, br.s), 4.86 (2H,
s), 3.81 (3H, s), 3.77 (3H, s), 2.24 (3H, s).

[0150]

Working Example 51 Methyl N- [2-methyl-4- {3-}
(2-trifluoromethylphenyl) pro-2-pinyloxydiphenyl] carbamate (Compound No. 8.4
7) Melting point: 91-94 ° C ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.67-7.41
(5H, m), 6.91-6.85 (2H, m), 6.19 (1H, br.s), 4.92
(2H, s), 3.77 (3H, s), 2.24 (3H, s).

[0151]

Example 52: Methyl N- [2-methyl-4- {3-}
(3-trifluoromethylphenyl) pro-2-pinyloxydiphenyl] carbamate (Compound No. 8.4
8) Melting point: 94-95 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.69 (1H,
br.s), 7.62-7.55 (2H, m), 7.47-7.34 (1H, m), 6.90-
6.85 (3H, m), 6.21 (1H, br.s), 4.89 (2H, s), 3.77
(3H, s), 2.25 (3H, s).

[0152]

Working Example 53 Methyl N- [2-methyl-4- {3-}
(4-trifluoromethylphenyl) pro-2-pinyloxydiphenyl] carbamate (Compound No. 8.4
9) Melting point: 115-117 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.60-7.50
(4H, m), 6.91-6.85 (3H, m), 6.21 (1H, br.s), 4.89
(2H, s), 3.77 (3H, s), 2.25 (3H, s).

[0153]

Example 54 Methyl N- [4- {3- (2-furyl) pro-2-pinyloxy} -2-methylphenyl]
Carbamate (Compound No. 8.50) Melting point: 99-101 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.55 (1H,
br.s), 7.38 (1H, d, J = 1.8Hz), 6.88-6.83 (2H, m),
6.61 (1H, d, J = 3.3Hz), 6.38 (1H, dd, J = 3.3,1.8Hz),
6.19 (1H, br.s), 4.89 (2H, s), 3.77 (3H, s), 2.24
(3H, s).

[0154]

Example 55 Methyl N- [4- {3- (3-furyl) pro-2-pinyloxy} -2-methylphenyl]
Carbamate (Compound No. 8.51) Melting point: 87-89 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.61 (1H,
s), 7.55-7.49 (1H, m), 7.36 (1H, t, J = 1.7Hz), 6.8
8-6.80 (2H, m), 6.43 (1H, d, J = 1.7Hz), 6.19 (1H, b
rs), 4.83 (2H, s), 3.77 (3H, s), 2.24 (3H, s).

[0155]

Working Example 56 Methyl N- [2-methyl-4- {3-}
(5-methyl-2-furyl) pro-2-pinyloxy}
Phenyl] carbamate (Compound No. 8.52) Melting point: 96-97 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.54-7.49
(1H, m), 6.87-6.82 (2H, m), 6.51 (1H, d, J = 3.3H
z), 6.22 (1H, br.s), 5.96 (1H, d, J = 3.3Hz), 4.88
(2H, s), 3.76 (3H, s), 2.29 (3H, s), 2.23 (3H, s).

[0156]

Example 57 Methyl N- [2-methyl-4- {3-
(2-thienyl) pro-2-pinyloxydiphenyl]
Carbamate (Compound No. 8.60) Melting point: 106-108 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.53 (1H,
br.s), 7.28-7.21 (2H, m), 6.99-6.94 (1H, m), 6.89-
6.84 (2H, m), 6.19 (1H, br.s), 4.89 (2H, s), 3.77
(3H, s), 2.25 (3H, s).

[0157]

Working Example 58 Methyl N- [2-methyl-4- {3-
(3-pyridyl) pro-2-pinyloxydiphenyl]
Carbamate (Compound No. 8.71) Melting point: 130-132 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 8.67 (1H,
d, J = 2.0Hz), 8.56-8.53 (1H, m), 7.72 (1H, td, J =
(7.8, 2.0Hz), 7.56 (1H, br.s), 7.27-7.20 (1H, m), 6.
91-6.85 (2H, m), 6.22 (1H, br.s), 4.89 (2H, s), 3.
77 (3H, s), 2.25 (3H, s).

[0158]

Working Example 59 Methyl N- [2-methyl-4- {3-}
(5-Methyl-2-pyridyl) pro-2-pinyloxydiphenyl] carbamate (Compound No. 8.75) Melting point: 137-140 ° C ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 8.40 (1H ,
s), 7.54-7.42 (2H, m), 7.32 (1H, d, J = 8.0Hz), 6.9
1-6.80 (2H, m), 6.24 (1H, br.s), 4.88 (2H, d, J = 3.
5Hz), 3.76 (3H, s), 2.34 (3H, s), 2.24 (3H, s).

[0159]

Working Example 60 Methyl N- [4- {3- (1H-pyraz-4-yl) pro-2-pinyloxy} phenyl] carbamate (Compound No. 8.86) Melting point: 172 ° -173 ° C. ¹ H-NMR spectrum (200MHz, CDCl ₃ ) δ (ppm): 9.23 (1H,
br.s), 8.02 (1H, d, J = 6.8Hz), 7.83-7.76 (1H, m),
7.60-7.54 (1H, m), 7.39 (2H, d, J = 8.6Hz), 6.89 (2
(H, d, J = 8.6Hz), 4.85 (2H, s), 3.69 (3H, s).

[0160]

Example 61 Methyl N- [4- {3- (benzoxazo-2-yl) pro-2-pinyloxy} -2-methylphenyl] carbamate (Compound No. 8.94) Melting point: 136-137 ° C ¹ H- NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.76-7.71
(1H, m), 7.60-7.36 (4H, m), 6.91-6.85 (2H, m), 6.
21 (1H, br.s), 4.95 (2H, s), 3.77 (3H, s), 2.25 (3
H, s).

[0161]

Example 62: Methyl N- [4- {3- (benzothiazo-2-yl) pro-2-pinyloxy} -2-methylphenyl] carbamate (Compound No. 8.95) Melting point: 133-134 ° C ¹ H- NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 8.05 (1H,
d, J = 7.6Hz), 7.84 (1H, d, J = 7.6Hz), 7.55-7.40 (3
H, m), 6.88-6.84 (2H, m), 6.36 (1H, br.s), 4.94 (2
H, s), 3.75 (3H, s), 2.24 (3H, s).

[0162]

Example 63 Methyl N- [4- {3- (2-fluorophenyl) pro-2-phenyloxy} phenyl] carbamate (Compound No. 6.4) Melting point: 164-166 ° C. ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 7.42-7.24
(4H, m), 7.02 (2H, t, J = 8.7Hz), 6.91 (2H, d, J = 9.1
Hz), 6.70 (1H, d, J = 15.9Hz), 6.45 (1H, br.s), 6.32
(1H, td, J = 16.1, 5.6Hz), 4.66 (2H, dd, J = 5.7, 1.4
Hz), 3.77 (3H, s).

[0163]

Example 64 Methyl N- [2-methyl-4- {3-
(5-Methyl-2-pyridyl) pro-2-phenyloxydiphenyl] carbamate (Compound No. 6.45) Melting point: 115-117 ° C ¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ (ppm): 8.39 (1H ,
d, J = 2.1Hz), 7.50-7.41 (2H, m), 7.21 (1H, d, J = 8.
1Hz), 6.85-6.72 (4H, m), 6.25 (1H, br.s), 4.71 (2
(H, d, J = 3.5Hz), 3.76 (3H, s), 2.32 (3H, s), 2.23
(3H, s).

[0164]

Formulation Example 1 wettable powder The compound described in Example 1 (Exemplary Compound No. 3.2) 25
%, Dodecylbenzenesulfonic acid sodium salt 2.5
%, 2.5% calcium ligninsulfonate and 70% diatomaceous earth were thoroughly pulverized and mixed to obtain a wettable powder.

[0165]

Formulation Example 2 Emulsion Compound (Exemplified Compound No. 3.2) 30 described in Example 1
%, Dodecylbenzenesulfonic acid calcium salt 2.68
%, Polyeoxyethylene alkyl ether 4.92
%, 0.4% of polyoxyethylene nonylphenyl ether calcium phosphate and 62% of xylene are mixed well to obtain an emulsion.

[0166]

Formulation Example 3 Granules Compound (Exemplified Compound No. 3.2) 5 described in Example 1
%, White carbon 1%, calcium ligninsulfonate 5%, bentonite 20% and clay 69% are thoroughly pulverized and mixed, water is added and kneaded well, and the mixture is granulated and dried to obtain granules.

[0167]

Formulation Example 4 Hydrated Granules Compound (Exemplified Compound No. 3.2) 80 described in Example 1
%, Special polycarboxylic acid polymer sodium salt 1.25
%, 3.75% water, 3% sodium dodecylbenzenesulfonate, 7% dextrin and 5% titanium oxide, then pulverize in an air mill, add into a rotary mixer or fluid bed mixer, spray water. Granulate. When most of the granules reached 1.0-0.15 mm, the granules were taken out, dried and sieved. Grind the oversized material to obtain granules of 1.0-0.15 mm.

[0168]

Formulation Example 5 Aqueous suspension The compound described in Example 1 (Exemplary Compound No. 3.2) 25
Parts, sodium dioctyl sulfosuccinate 0.7
Parts, 0.15 parts of propylene glycol, 10 parts of calcium ligninsulfonate, 44.15 parts of water and 10 parts of propylene glycol in a ball mill, sand mill or roller mill until the solid particles are reduced to a diameter of 5 microns or less. Crush together. To 90 parts of this pulverized slurry, 10 parts of a 0.05% (W / W) xanthan gum aqueous solution is added and mixed to obtain an aqueous suspension.

[0169]

Test Example 1 Herbicidal Effect and Chemical Damage (Pre-emergence treatment of paddy weeds) A 100 cm ² pot was filled with paddy field soil, and the seeds of a sleepy awakened Aedes millet were mixed with 1 cm of the surface layer. In addition, rice seedlings of the two-leaf stage were transplanted into a flooded state and grown in a greenhouse. Three days later, a prescribed dose was applied to flooded soil using a wettable powder prepared according to Formulation Example 1, and 21 days later, the herbicidal effect on rice millet and the phytotoxicity on rice were investigated. Table 3 shows the results. The herbicidal effect and the phytotoxicity are represented by indices, and each index indicates the growth inhibition rate described in Table 2 below.

[0170]

[Table 2] Criteria 基準 Index of herbicidal effect and phytotoxicity Growth suppression rate ( %) ０ 00-10 1 11-30 2 31-50 3 51 -70 47 1-90 5 91-100

[0171]

[Table 3] Herbicidal effect and phytotoxicity ────────────────────────────────── Test compound (Compound No.) Pre-emergence treatment of paddy weeds (g / a) Rice flour Rice (herbicidal effect) (phytotoxicity) ─────────────────────────────── １ Example 1 (Compound No. 3.2) 20 50 Example 2 (Compound No. 3.35) 20 500 Example 4 (Compound No. 1.1) 20 500 Example 7 (Compound No. 3. 21) 20500 Example 9 (Compound No. 3.7) 20500 Example 10 (Compound No. 3.8) 20500 Example 20 (Compound No. 5.3) 20500 Example 21 (Compound No.) 5.4) 20 50 Example 22 (Compound No. 5.5) 20 50 Example 23 (Compound No. 5.6) 20 50 Example 24 (Compound No. 5.8) 2 0 500 Example 25 (Compound No. 5.34) 20 50 Example 26 (Compound No. 5.50) 20 50 Example 34 (Compound No. 5.60) 20 500 Example 35 (Compound No. 5.50) 71) 20500 Example 41 (Compound No. 8.1) 20500 Example 44 (Compound No. 8.4) 20500 Example 45 (Compound No. 8.5) 20500 Example 46 (Compound No.) 8.6) 20 50 Example 47 (Compound No. 8.8) 20 50 Example 48 (Compound No. 8.34) 20 50 Example 49 (Compound No. 8.35) 20 50 Example 50 ( Compound No. 8.36) 20 50 Example 52 (Compound No. 8.48) 20 50 Example 53 (Compound No. 8.49) 20 50 Example 54 (Compound No. 8.50) 20 500 Example 55 (Compound No. 8.51) 20 50 Example 7 (Compound No. 8.60) 20 50 Example 58 (Compound No. 8.71) 20 50 Example 63 (Compound No. 6.4) 20 500化合物 The herbicidal effect of the tested compound is “5”, the phytotoxicity is “0”, and

[0172]

Embedded image Comparative compound represented by the following formula: Compound disclosed in Example 1 in JP-A-8-157435 (exemplary compound number 1.1)
As compared with the compound と し て described in Table 1.

[0173]

The compound of the present invention has a herbicidal action and can be used as a herbicide. For example, in a paddy field, by treating a flooded soil before or after germination of a weed, it is possible to strongly control grass weeds, such as the rice weeds, such as the rice breeder, the barnyardgrass, and the canine millet, which are the strong weeds of the paddy field.

On the other hand, the selectivity for rice is high.
Transplanted rice does not suffer from chemical injury, and thus has the advantage that the treatment application range is large.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Souji Morimoto 1041 Yasu, Yasu-cho, Yasu-gun, Shiga Prefecture Sankyo Stock Company In-house

Claims (20)

[Claims] 1. A compound represented by the following general formula (I): [Wherein, R ¹ represents a C1-C6 alkyl group (the alkyl group may be substituted by a halogen atom), and R ² represents a hydrogen atom, a C1-C6 alkyl group (the alkyl group is Hydroxyl group, C1-C6 alkoxy group, C1-
It may be substituted by a C6 alkylthio group or a C1-C6 alkylsulfonyl group. ), C3 -C6 alkenyl group, a C3 -C6 alkynyl group or a benzyl group, Z is a group represented by the nitrogen atom or the formula -C (R ^3a), R ^3a is a hydrogen atom, C1 -C6 Alkyl group, C1
~C6 an alkoxy group or a halogen atom, R ³ is
A C1-C6 alkyl group, a C1-C6 alkoxy group or a halogen atom, and n represents 0, 1, 2, or 3 (however, when n is 2 or 3, each R ³ is the same or different And adjacent R ³ may be taken together to form a 5- or 6-membered ring.), R ⁴ and R ⁵
Are the same or different and each represent a hydrogen atom or a C1-C6 alkyl group, and A is a group represented by the formula -C≡C- or a formula-
C (R ⁶ ) = CH- (wherein R ⁶ is a hydrogen atom, C 1 -C
6 represents an alkyl group or a halogen atom. Q is a C6-C10 aryl group [the aryl group is a C1-C6 alkyl group (the alkyl group may be substituted by a halogen atom); a C1-C6 alkoxy group] Or a phenoxy group, a halogen atom, a nitro group and a cyano group, and may be substituted by 1 to 5 identical or different substituents. Or a heterocyclic group containing at least one oxygen, sulfur or nitrogen atom and having 3 to 10 ring atoms (the heterocyclic group is preferably 1 to 4 identical or different halogen atoms, 1 to 3 (It may be substituted by the same or different C1 to C6 alkyl group or 1 to 3 same or different C1 to C6 alkoxy groups, or may be condensed with a benzene ring.)
Is shown. ] The aminophenol derivative represented by these, or its salt. 2. The aminophenol derivative according to claim 1, wherein R ¹ is a C1-C4 alkyl group (the alkyl group may be substituted by a halogen atom) or a salt thereof. 3. The aminophenol derivative or a salt thereof according to claim 1, wherein R ¹ is a methyl group or an ethyl group (the methyl group or the ethyl group may be substituted by a chlorine atom). 4. The aminophenol derivative or a salt thereof according to claim 1, wherein R ¹ is a methyl group. 5. The method according to claim 1, wherein R ² is a hydrogen atom or a C1 to C4 alkyl group (the alkyl group may be substituted by a hydroxyl group or a C1 to C4 alkoxy group). Or a salt thereof. 6. The aminophenol derivative or a salt thereof according to claim 1, wherein R ² is a hydrogen atom. 7. The aminophenol derivative or a salt thereof according to claim 1, wherein Z is a nitrogen atom or a group represented by the formula —CH. 8. The aminophenol derivative or a salt thereof according to claim 1, wherein Z is a group represented by the formula —CH. 9. R ³ is, C1 -C4 alkyl group, C1～C
9. The aminophenol derivative or a salt thereof according to claim 1, which is a 3 alkoxy group or a halogen atom, and n is 0 or 1. 10. The aminophenol derivative or a salt thereof according to claim 1, wherein R ³ is a methyl group, a methoxy group or a fluorine atom, and n is 1. 11. The method according to claim 1, wherein R ⁴ and R ⁵ are the same or different and each is a hydrogen atom or a C1 to C4 alkyl group.
Or the salt thereof. 12. The aminophenol derivative or a salt thereof according to claim 1, wherein R ⁴ and R ⁵ are the same or different and each is a hydrogen atom, a methyl group or an ethyl group. 13. The aminophenol derivative or a salt thereof according to claim 1, wherein R ⁴ and R ⁵ are both hydrogen atoms. 14. A is a group represented by the formula —C≡C— or a formula —C (R ⁶ ) ＝ CH— (where R ⁶ is a hydrogen atom,
It represents a C4 alkyl group or a halogen atom. The aminophenol derivative or a salt thereof according to any one of claims 1 to 13, which is a group represented by the formula: 15. A is a group represented by the formula —C≡C— or a formula —C (R ⁶ ) ＝ CH— (wherein R ⁶ represents a hydrogen atom or a chlorine atom). The aminophenol derivative or a salt thereof according to any one of claims 1 to 13, which is a group represented by the formula: 16. The aminophenol derivative or a salt thereof according to claim 1, wherein A is a group represented by the formula —C≡C—. (17) Q is a phenyl group [the phenyl group is
A C1-C4 alkyl group (the alkyl group may be substituted with a halogen atom), a C1-C3 alkoxy group and a substituent substituted with 1 to 5 identical or different substituents selected from the group consisting of a halogen atom; You may. ]
Or a heterocyclic group containing at least one oxygen, sulfur or nitrogen atom and having 3 to 6 ring atoms (the heterocyclic group is 1 to 4 identical or different halogen atoms, and 1 to 3 identical Or a different C1-C4 alkyl group or 1
It may be substituted by up to three identical or different C1-C3 alkoxy groups, or may be condensed with a benzene ring. ). ] The aminophenol derivative or a salt thereof according to any one of claims 1 to 16. 18. A phenyl group which may be substituted by 1 to 5 same or different substituents selected from the group consisting of a methyl group, a trifluoromethyl group, a methoxy group, a chlorine atom and a fluorine atom, The aminophenol derivative or a salt thereof according to any one of claims 1 to 16, which is a furyl group, a thienyl group or a pyridyl group. 19. The aminophenol derivative is methyl N- {2-methyl-4- (3-phenylpro-
2-Pinyloxy) phenyl {carbamate, methyl N- {2- (3-phenylpro-2-pinyloxy) pyridin-5-yl} carbamate, methyl N- {4- (3-phenylpro-2-pinyloxy) phenyl} Carbamate, methyl N- {2-methoxy-4- (3-phenylpro-2-pinyloxy) phenyl} carbamate, methyl N- {2-fluoro-4- (3-phenylpro-2-pinyloxy) phenyl} carbamate, Methyl N- {2-chloro-4- (3-phenylpro-
2-Pinyloxy) phenyl} carbamate, methyl N- [4- {3- (4-methylphenyl) pro-2-pinyloxy} phenyl] carbamate, methyl N- [4- {3- (2-fluorophenyl) pro- 2-Pinyloxy} phenyl] carbamate, methyl N- [4- {3- (3-fluorophenyl) pro-2-pinyloxy} phenyl] carbamate, methyl N- [4- {3- (4-fluorophenyl) pro- 2-Pinyloxy} phenyl] carbamate, methyl N- [4- {3- (2,4-difluorophenyl) pro-2-pinyloxy} phenyl] carbamate, methyl N- [4- {3- (2-methoxyphenyl) Pro-2-pinyloxy {phenyl] carbamate, methyl N- [4- {3- (2-furyl) pro-2-] Niruokishi} phenyl] carbamate, methyl N- [4- {3- (2- thienyl) pro -2-
Pinyloxy {phenyl] carbamate, methyl N- [4- {3- (3-pyridyl) pro-2-
Pinyloxy {phenyl] carbamate, methyl N- [2-methyl-4- {3- (2-methylphenyl) pro-2-pinyloxy} phenyl] carbamate, methyl N- [4- {3- (2-fluorophenyl) Pro-2-pinyloxy {-2-methylphenyl] carbamate, methyl N- [4- {3- (3-fluorophenyl) pro-2-pinyloxy} -2-methylphenyl] carbamate, methyl N- [4-} 3- (4-fluorophenyl) pro-2-pinyloxy {-2-methylphenyl] carbamate, methyl N- [4- {3- (2,4-difluorophenyl) pro-2-pinyloxy} -2-methylphenyl ]
Carbamate, methyl N- [4- {3- (2-methoxyphenyl) pro-2-pinyloxy} -2-methylphenyl] carbamate, methyl N- [4- {3- (3-methoxyphenyl) pro-2- Pinyloxy {-2-methylphenyl] carbamate, methyl N- [4- {3- (4-methoxyphenyl) pro-2-pinyloxy} -2-methylphenyl] carbamate, methyl N- [2-methyl-4-} 3- (3-trifluoromethylphenyl) pro-2-pinyloxy {phenyl] carbamate, methyl N- [2-methyl-4- {3- (4-trifluoromethylphenyl) pro-2-pinyloxy} phenyl] carbamate Methyl N- [4- {3- (2-furyl) pro-2-pinyloxy} -2-methylphenyl] carbamate Methyl N- [4- {3- (3-furyl) pro-2-pinyloxy} -2-methylphenyl] carbamate, methyl N- [2-methyl-4- {3- (2-thienyl) pro-2- Pinyloxy {phenyl} carbamate, methyl N- [2-methyl-4- {3- (3-pyridyl) pro-2-pinyloxy} phenyl] carbamate or methyl N- [4- {3- (2-fluorophenyl) pro An aminophenol derivative or a salt thereof according to any one of claims 1 to 18, which is [-2-phenyloxydiphenyl] carbamate. 20. A herbicide comprising the aminophenol derivative according to claim 1 or a salt thereof as an active ingredient.