JPH08157435A - Herbicidal aminophenol derivative - Google Patents

Abstract

PURPOSE: To obtain the subject new compound presenting virtually no chemical injuries no paddy rice, presenting, in contrast, excellent herbicidal activity at low doses on Echinochloa oryzicola, a kind of persistent paddy weed, thus useful as a herbicide, esp. for applying to paddy fields. CONSTITUTION: This new compound is expressed by formula I [R<1> is a (halogen- substituted) 1-6C alkyl; R<2> is H, a (1-6C alkylthio-substituted) 1-6C alkyl, 3-6C alkenyl, etc.; R<3> is a 1-6C alkyl, 1-6C alkoxyl or halogen; R<4> is H or a 1-6C alkyl; R<5> is a 1-6C alkyl, 1-6C alkoxyl, phenoxy, etc.; A is C≡C or a group of formula CR<6> =CH (R<6> is H, a 1-6C alkyl or halogen); n is 0-4; m is 0-5], e.g. O-phenylpropargyl-4-acetamidophenol. The compound of formula I is obtained by reaction of a compound of formula II with a compound of formula III (X<1> is an eliminable group) to form a compound of formula IV which is, if needed, reacted with a compound of formula R<2a> X<2> (X<2> is the same as X<1> ; R<2a> is the same as R<2> except H).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel aminophenol derivative having excellent herbicidal activity and a herbicidal composition containing it as an active ingredient.

[0002]

2. Description of the Related Art As aminophenol derivatives, 1,1-dimethyl-3- (4-phenylpropargyloxyphenyl) urea (USP 4,289,90) has hitherto been known.
3) and 1,1-dimethyl-3- {4- (2-methylcinnamoyloxy) phenyl} urea (JP-A-59-1)
No. 93810) are known to have upland herbicidal activity.

However, these compounds differ from the compounds of the present invention in that they have a urea partial structure. Further, while the compound of the present application exhibits excellent herbicidal activity against fly, and is useful as a herbicide for paddy field, the compound of the prior art has low potency against fly and is not useful as a herbicide for paddy field, that is, herbicidal spectrum. From the point of
It's completely different.

[0004]

DISCLOSURE OF THE INVENTION As a result of years of earnest research on the synthesis and biological activity of aminophenol derivatives, the present inventor found that a novel aminophenol derivative having a structure different from that of a known compound was found. The present invention has been completed, and it was found that they show almost no phytotoxicity to paddy rice, and that they show excellent herbicidal activity at a low dose against Tainubie, which is a highly damaging weed in paddy fields.

[0005]

Configuration of the Invention

[0006]

The present invention has the following general formula (I):

[0007]

Embedded image

[In the formula, R ¹ represents a C1 to C6 lower alkyl group (the lower alkyl group may be substituted with a halogen atom), R ² represents a hydrogen atom, a C1 to C6 lower alkyl group ( The lower alkyl group may be substituted with a C1 to C6 lower alkylthio group or a C1 to C6 lower alkylsulfonyl group), a C3 to C6 lower alkenyl group, a C3 to C6 lower alkynyl group, a phenylpropargyl group (the phenyl group). Is a halogen atom, C1
C6 lower alkyl group or C1 to C6 lower alkoxy group may be substituted) or benzyl group, R
³ is C1 -C6 lower alkyl group, a C1 -C6 lower alkoxy group or a halogen atom, R ⁴ represents a hydrogen atom or a C1 -C6 lower alkyl group, R ⁵ is C1～C
6 lower alkyl group, C1 to C6 lower alkoxy group, phenoxy group, halogen atom or trifluoromethyl group, A is a group represented by the formula —C≡C— or a formula —C (R
⁶⁾ = CH- a group represented by (R ⁶ is a hydrogen atom, C1 to
C6 lower alkyl group or halogen atom) is shown,
n is 0 or an integer of 1 to 4 (provided that n is 2 to 4)
In the case of, each R ³ may be the same or different, and m is 0 or an integer of 1 to 5 (provided that m is 2).
In the case of 1 to ⁵ , each R ⁵ may be the same or different). ], Preferably, [wherein R ¹ represents a C1-C4 lower alkyl group (the lower alkyl group may be substituted with a halogen atom), and R ² represents Hydrogen atom, C1-C4 lower alkyl group, C3-C5 lower alkenyl group, C3-C5
A lower alkynyl group, a phenylpropargyl group (the phenyl group may be substituted with a halogen atom, a C1 to C4 lower alkyl group or a C1 to C3 lower alkoxy group) or a benzyl group, and R ³ represents C1 to C4. lower alkyl group, a C1~C3 lower alkoxy group or a halogen atom, R ⁴ represents a hydrogen atom or a C1 -C4 lower alkyl group, R ⁵ is C1 -C4 lower alkyl groups, C
1 to C3 is a lower alkoxy group, a phenoxy group or a halogen atom, and A is a group represented by the formula -C≡C- or a formula-
A group represented by C (R ⁶ ) ═CH— (R ⁶ is a hydrogen atom,
C1 to C4 is a lower alkyl group or a halogen atom, and n is 0 or an integer of 1 to 4 (where n is 2).
In the case of 4 to 4, each R ³ may be the same or different), m is 0 or an integer of 1 to 5 (provided that
When m is 2 to 5, each R ⁵ may be the same or different). ], More preferably, [wherein R ¹ represents a methyl group (the methyl group may be substituted with a fluorine atom or a chlorine atom), and R ² represents hydrogen] An atom or a phenylpropargyl group (the phenyl group may be substituted with a fluorine atom, a chlorine atom or a methoxy group), and R ³ is
A methyl group or a chlorine atom, R ⁴ represents a hydrogen atom, R ⁵ represents a methyl group, a methoxy group, a fluorine atom or a chlorine atom, and A represents a group represented by the formula —C≡C— or Expression −
C (R ⁶ ) ═CH— represents a group (R ⁶ represents a hydrogen atom or a chlorine atom), n represents 0, 1 or 2 (provided that when n is 2, each R ³ may be the same or different, and m represents 0, 1 or 2 (provided that
When m is 2, each R ⁵ may be the same or different). ] More preferably, the aminophenol derivative represented by the formula [wherein R ¹ represents a methyl group or a fluoromethyl group, R ² represents a hydrogen atom, and R ³ represents
Represents a methyl group, R ⁴ represents a hydrogen atom, R ⁵ represents a methoxy group, a fluorine atom or a chlorine atom, and A represents a formula —C.
Represents a group represented by ≡C-, n represents 0, 1 or 2 (provided that when n is 2, each R ³ may be the same or different), m is 0, 1 or 2 (however,
When m is 2, each R ⁵ may be the same or different). ] The aminophenol derivative represented by these, and a herbicide containing these aminophenol derivatives as an active ingredient.

In the above, the "halogen atom" is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. R ¹
In the substitution of the lower alkyl group of R ² , the substitution of the phenylpropargyl group of R ² , and R ³ and R ⁵ , a fluorine atom or a chlorine atom is preferable. R ⁶ is preferably a chlorine atom or an iodine atom.

In the above, "C1-C6 lower alkyl group" means, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, 2 -Methylbutyl, neopentyl, 1-ethylpropyl, n-hexyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1, A linear or branched alkyl group having 1 to 6 carbon atoms such as 1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 2-ethylbutyl It is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 4 carbon atoms (C1 to C4 lower alkyl group). Yes, more preferably 1 to 2 carbon atoms An alkyl group, and most preferably a methyl group.

In the above, "C3-C6 lower alkenyl group" means, for example, 2-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-ethyl-2-propenyl, 2-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-4-pentenyl, 2-methyl-4-pentenyl, 2-
A linear or branched alkenyl group having 3 to 6 carbon atoms, such as hexenyl, 3-hexenyl, 4-hexenyl, and 5-hexenyl, preferably a linear or branched chain having 3 to 5 carbon atoms A chain alkenyl group (C3-C5 lower alkenyl group), and more preferably a 2-propenyl group.

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

In the above, "C1-C6 lower alkoxy group" means, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, n-pentoxy, isopentoxy,
2-methylbutoxy, neopentoxy, 1-ethylpropoxy, n-hexyloxy, 4-methylpentoxy, 3-methylpentoxy, 2-methylpentoxy, 1-methylpentoxy, 3,3-dimethylbutoxy, 2, 2-dimethylbutoxy, 1,
A linear or branched alkoxy group having 1 to 6 carbon atoms such as 1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,3-dimethylbutoxy, 2-ethylbutoxy. It is preferably a linear or branched alkoxy group having 1 to 3 carbon atoms (C1 to C3 lower alkoxy group), and more preferably a methoxy group or an ethoxy group.

In the above, "C1-C6 lower alkylthio group" means, for example, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, s-butylthio, t-butylthio, n-pentylthio, iso- Pentylthio, 2-methylbutylthio, neopentylthio, 1-ethylpropylthio, n-hexylthio, 4-
Methylpentylthio, 3-methylpentylthio, 2-methylpentylthio, 1-methylpentylthio, 3,3-dimethylbutylthio, 2,2-dimethylbutylthio, 1,1-dimethylbutylthio, 1,2- A lower alkylthio group having 1 to 6 carbon atoms, such as dimethylbutylthio, 1,3-dimethylbutylthio, 2,3-dimethylbutylthio, 2-ethylbutylthio group, preferably 1 to 6 carbon atoms. Three linear or branched alkylthio groups are preferred, and methylthio and ethylthio groups are more preferred.

In the above, "C1-C6 lower alkylsulfonyl group" means, for example, methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, s-butylsulfonyl, t-butyl. Sulfonyl, n-pentylsulfonyl, isopentylsulfonyl, 2-methylbutylsulfonyl, neopentylsulfonyl, 1-ethylpropylsulfonyl, n-hexylsulfonyl, 4-methylpentylsulfonyl, 3-methylpentylsulfonyl, 2-methylpentylsulfonyl, 1-methylpentylsulfonyl, 3,3-dimethylbutylsulfonyl, 2,2-dimethylbutylsulfonyl, 1,1-dimethylbutylsulfonyl, 1,2-dimethylbutylsulfonyl, 1,3-dimethylbutylsulfonyl, 2,3- Dimethylbutylsulfonyl, 2- A lower alkylsulfonyl group having 1 to 6 carbon atoms such as a butylbutylsulfonyl group, preferably a linear or branched alkylsulfonyl group having 1 to 3 carbon atoms, and more preferably methylsulfonyl group. , An ethylsulfonyl group.

C1 to C6 substituted by a halogen atom
The lower alkyl group is, for example, chloromethyl, dichloromethyl, trichloromethyl, 1-chloroethyl, 2-chloroethyl, 1-chloropropyl, 3-chloropropyl, 1-chlorobutyl, 4-chlorobutyl, fluoromethyl, difluoromethyl, trifluoromethyl. , 1-fluoroethyl, 2-
Fluoroethyl, fluorochloromethyl, bromomethyl, 1-bromomethyl, 2-bromoethyl is a group in which 1 to 4 of the above "halogen atoms" are bonded to the above "C1 to C6 lower alkyl group", and preferably fluoro It is a methyl group.

In the above general formula (I), R ¹ is preferably a methyl group or an ethyl group (the methyl group or ethyl group may be substituted with a fluorine atom), and more preferably, It is a methyl group or a fluoromethyl group.

In the above general formula (I), R ² is preferably a hydrogen atom or a phenylpropargyl group (the phenyl group is substituted with a halogen atom, a C1 to C6 lower alkyl group or a C1 to C6 lower alkoxy group). May be present), and more preferably a hydrogen atom.

In the above general formula (I), R ³ is preferably a C1 to C6 lower alkyl group or a halogen atom, and more preferably a methyl group.

In the above general formula (I), R ⁴ is preferably a hydrogen atom, a methyl group or an ethyl group, and more preferably a hydrogen atom.

In the above general formula (I), R ⁵ is preferably a C1 to C6 lower alkyl group, a C1 to C6 lower alkoxy group or a halogen atom, and more preferably a methoxy group or a halogen atom. .

In the above general formula (I), A is preferably a group represented by the formula —C≡C—.

In the above general formula (I), R ⁶ is preferably a hydrogen atom or a halogen atom.

In the above general formula (I), n and m are
It is preferably 0, 1 or 2, and more preferably 0 or 2.

Representative compounds of the present invention are shown in Tables 1 to 7 below, but the present invention is not limited to these compounds.

Hereinafter, Me is a methyl group, Et is an ethyl group, nPr is an n-propyl group, iPr is an isopropyl group, nBu is an n-butyl group, and Ph is a phenyl group.
Shown respectively.

In the columns R ³ and R ⁵ , the number before the substituent indicates the substitution position of the substituent, and the subscript number after the substituent indicates the number of substitutions of the substituent. For example, 2
-CF ₃ is trifluoromethyl group substituted at the 2-position, 2, 4-Cl ₂ is 2,4-dichloro group.

[0028]

[Table 1]

[0029]

[Chemical 6]

───────────────────────────────────── Compound No. R ¹ Physical properties (℃) ─── ───────────────────────────────── 1.1 Me 135-139 1.2 Et 121-123 1.3 nPr 107-110 1.4 nBu 86-88 1.5 iPr 1.6 CH ₂ F 128-129 1.7 CH ₂ Cl 130-131 1.8 CHCl ₂ 140-142 1.9 CF ₃ 135-138 1 10 CH ₂ Br 1.11 CHClF ─────────────────────────────────────

[0031]

[Table 2]

[0032]

[Chemical 7]

──────────────────────────────────── Compound number R ² (R ⁵ ) _m Physical properties ( ℃) ──────────────────────────────────── 2.1 Me H 90-91 2.2 CH ₂ CH = CH ₂ H 81-84 2.3 CH ₂ C≡CH H 93-97 2.4 CH ₂ Ph H oil 2.5 CH ₂ SMe H amorphous 2.6 CH ₂ SO ₂ Me H 120-122 2 0.7 CH ₂ C≡CPh H 2.8 CH ₂ C≡C (4-F-Ph) H 2.9 CH ₂ C≡C (4-F-Ph) 4-F 2.10 CH ₂ C≡C (4-OMe-Ph) 4-OMe oil 2.11 CH ₂ C≡C (4-Me-Ph) 4-Me 165-170 ─────────────────── ──────────────────

[0034]

[Table 3]

[0035]

Embedded image

──────────────────────────────────── Compound number (R ³ ) _n Physical properties (℃) ──────────────────────────────────── 3.1 3-Me 73-75 3.2 2- Me 146-148 3.3 2,3- (Me) ₂ 180-183 3.4 2,5- (Me) ₂ 160-162 3.5 3,5- (Me) ₂ amorphous 3.6 2,6 -(Me) ₂ 3.7 2-F 3.8 2-Cl 3.9 3-F 3.10 3-Cl 118-119 3.11 2,3-F ₂ 3.12 2,3-Cl ₂ 3.13 2,5-F ₂ 3.14 2,5-Cl ₂ 150-155 3.15 3,5-F ₂ 3.16 3,5-Cl ₂ 201-204 3.17 2,6-F _{2 3.18 2,6-Cl 2 3.19 2} -Me, 5-Cl 169-171 3.20 2-OMe, 5-Cl 138-139 ───────────────────────────────────

[0037]

[Table 4]

[0038]

[Chemical 9]

──────────────────────────────────── Compound No. R ⁴ Physical property (℃) ─── ───────────────────────────────── 4.1 Me 124-128 4.2 Et 78-80 ─── ──────────────────────────────────

[0040]

[Table 5]

[0041]

[Chemical 10]

──────────────────────────────────── Compound number (R ⁵ ) _m Physical properties (℃) ──────────────────────────────────── 5.1 2-Me 5.2 5.2 3-Me 96- 97 5.3 4-Me 215-218 5.4 2-F 160-162 5.5 3-F 110-116 5.6 4-F 155-157 5.7 2,3-F ₂ 5.8 2 , 4-F ₂ 115-117 5.9 2,5-F ₂ 115-118 5.10 2,6-F ₂ 182-183 5.11 3,4-F ₂ 5.12 3,5-F ₂ 5.13 2,3,5-F ₃ 5.14 2,4,6-F ₃ 5.15 2,4,5-F ₃ 5.16 2,3,6-F ₃ 5.17 2,3 _{, 5,6-F 4 5.18 2,3,4,5,6-} F 5 5.19 2-Cl 133-135 5.20 3-Cl 5.21 4-Cl 170-180 5.22 _{, 3-Cl 2 5.23 2,4-} Cl 2 110-112 5.24 2,5-Cl 2 5.25 2,6-Cl 2 5.26 3,4-Cl 2 5.27 3,5 _{-Cl 2 5.28 2,3,5-Cl 3 5.29} 2,4,6-Cl 3 5.30 2,4,5-Cl 3 5.31 2,3,6-Cl 3 5.32 2-Cl, 4-F 143-146 5.33 2-F, 6-Cl 168-170 5.34 2-OMe 114-115 5.35 3-OMe 77-78 5.36 4-OMe 165-170 5.37 2,3- (OMe) ₂ 104-105 5.38 2,4- (OMe) ₂ oil 5.39 2,5- (OMe) ₂ 107-109 5.40 2,6- (OMe) _{2 5.41 3,4- (OMe) 2 100-102} 5.42 3,5- (OMe) 2 94-95 5.43 2-OEt 94-96 5.44 4-OEt 73-75 5.45 3-OPh 72-74 5.46 4-OPh 128-132 5 .47 2-CF ₃ 108-112 5.48 3-CF ₃ 5.49 4-CF ₃ ──────────────────────────── ─────────

[0043]

[Table 6]

[0044]

[Chemical 11]

──────────────────────────────────── Compound number (R ⁵ ) _m Physical property (℃) ──────────────────────────────────── 6.1 H 170-172 6.2 2-F 6 .3 3-F 6.4 4-F 6.5 2,3-F ₂ 6.6 2,4-F ₂ 162-164 6.7 2,5-F ₂ 143-145 6.8 2,6 _{-F 2 105-108 6.9 3,4-F 2} 6.10 3,5-F 2 6.11 2,3,5-F 3 6.12 2,4,6-F 3 6.13 2 _{, 4,5-F 3 6.14 2,3,6-} F 3 6.15 2,3,5,6-F 4 6.16 2,3,4,5,6-F 5 6.17 2 -Cl 120-121 6.18 3-Cl 6.19 4-Cl 6.20 2,3-Cl ₂ 6.21 2,4-Cl ₂ 6.22 2,5-Cl ₂ 6.23 2,6-Cl ₂ 6.24 3,4-Cl ₂ 6.25 3,5-Cl ₂ 6.26 2,3,5-Cl ₃ 6.27 2,4,6-Cl ₃ 6.28 2 , 4,5-Cl ₃ 6.29 2,3,6-Cl ₃ 6.30 2-Cl, 4-F 134-137 6.31 2-F, 6-Cl 98-100 ────── ──────────────────────────────

[0046]

[Table 7]

[0047]

[Chemical 12]

──────────────────────────────────── Compound No. R ² R ⁶ (R ⁵ ) _m Physical properties (℃) ──────────────────────────────────── 7.1 H Cl H 102-104 7 .2 H Cl H 108-110 7.3 H Cl 2-F 90-92 7.4 H Cl 3-F 7.5 H Cl 4-F 142-143 7.6 H Cl 2,3-F ₂ 7 .7 H Cl 2,4-F ₂ 7.8 H Cl 2,5-F ₂ 7.9 H Cl 2,6-F ₂ 7.10 H Cl 3,4-F ₂ 7.11 H Cl 3, 5-F ₂ 7.12 H Cl 2-Cl 126-128 7.13 H Cl 3-Cl 7.14 H Cl 4-Cl 134-135 7.15 H Cl 4-Cl 142-143 7.16 H Cl 2,3-Cl ₂ 7.17 H Cl 2,4-Cl ₂ 7.18 H Cl 2, 5-Cl ₂ 7.19 H Cl 2,6-Cl ₂ 7.20 H Cl 3,4-Cl ₂ 7.21 H Cl 3,5-Cl ₂ 7.22 H Cl 2-Me 105-108 7. 23 H Cl 3-Me 7.24 H Cl 4-Me Amorphous 7.25 H Cl 4-Me 126-128 7.26 H Cl 2-OMe 140-143 7.27 H Cl 2-OMe 131 7.28 H Cl 3-OMe 7.29 H Cl 4-OMe 116-118 7.30 HI H 7.31 HI 2-F 7.32 HI 3-F 7.33 HI 4-F 7.34 HI 2,4-F ₂ 7.35 HI 2-Cl 7.36 HI 3-Cl 7.37 HI 4-Cl 7.38 HI 2,4-Cl ₂ 7.39 HI 2-OMe 7 .40 HI 2-OEt 110-112 7.41 HI 4-OEt 155-156 7.42 H Me H 7.43 H Me 2- 7.44 H Me 3-F 7.45 H Me 4-F 142-144 7.46 H Me 2-Cl 7.47 H Me 3-Cl 7.48 H Me 4-Cl 7.49 CH 2 C≡ CPh H H Oil 7.50 CH ₂ C≡C (4-F-Ph) H H 108-110 ─────────────────────────── ────────── 7.1, 7.14, 7.24, 7.26 are transformers.

7.2, 7.15, 7.25, 7.27
Is a cis form.

Nuclear magnetic resonance spectra of some of the compounds in the above table are shown below.

Compound 2.4 NMR (200 MHz, CDCl ₃ ) δ: 7.45-7.18 (10H,
m), 6.99-6.88 (4H, m), 4.90.
(2H, s), 4.85 (2H, s), 1.89
(3H, s). Compound 2.5 NMR (200 MHz, CDCl ₃ ) δ: 7.46-7.06
(9H, m), 4.95 (2H, s), 4.82 (2H, s), 2.17 (3H, s), 1.87 (3
H, s). Compound 2.10 NMR (200MHz, CDCl ₃ ) δ: 7.37 (2H, d, J = 8.9Hz), 7.30-7.2
3 (4H, m), 7.08 (2H, d, J = 8.9Hz), 6.80 (4H, t, J = 8.9Hz),
4.93 (2H, s), 4.67 (2H, s), 3.80 (3H, s), 3.78 (3H, s), 1.
88 (3H, s). Compound 3.5 NMR (200MHz, CDCl ₃ ) δ: 7.40-7.20 (7H, m), 6.95 (1H, br.
s), 4.65 (2H, s), 2.27 (6H, s), 1.89 (3H, s). Compound 5.38 NMR (200MHz, CDCl ₃ ) δ: 7.41 (2H, d, J = 9.0Hz), 7.35 -7.2
7 (1H, m), 7.09 (1H, br.s), 7.01 (2H, d, J = 9.0Hz), 6.42 (2
H, m), 4.91 (2H, s), 3.84 (3H, s), 3.80 (3H, s), 2.15 (3H,
s). Compound 7.24 NMR (200 MHz, CDCl ₃ ) δ: 7.45-6.98 (7H, m), 6.84 (2H, d, J
= 9.1Hz), 4.74 (2H, s), 2.35 (3H, s), 2.16 (3H, s). Compound 7.49 NMR (200MHz, CDCl ₃ ) δ: 7.45-7.21 (12H, m), 7.00 ( 2H, d,
J = 8.9Hz), 6.76 (1H, d, J = 15.9Hz), 6.42 (1H, dt, J = 15.9,
5.7Hz), 4.73 (2H, d, J = 5.7Hz), 4.69 (2H, s), 1.88 (3H,
s). Among the above exemplified compounds, preferred ones are 1.1,
1.6, 1.9, 2.11, 3.3, 3.5, 3.1
0, 4.2, 5.2, 5.3, 5.4, 5.5, 5.
6, 5.8, 5.9, 5.10, 5.19, 5.21,
5.32, 5.34, 5.36, 5.43, 5.44,
5.46, 6.1, 6.6, 6.7, 6.8, 6.1
7, 6.30, 7.1, 7.2, 7.15, 7.22,
The compounds of 7.24 and 7.25 can be mentioned.

More preferred are 1.1, 1.
6, 5.4, 5.5, 5.6, 5.8, 5.9, 5.1
The compounds of 0, 5.32, 5.34, 5.36 and 6.6 can be mentioned.

The most preferable compounds are 1.1, 5.
The compounds of Nos. 4,5.5 and 5.8 can be mentioned.

[0054]

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

(Method A)

[0056]

[Chemical 13]

During the above steps, R ¹ , R ³ , R ⁴ , R ⁵ ,
A, m and n are as defined above, X ¹ and X ² are the same or different and each represents a leaving group, and R ^2a is a C1 to C6 lower alkyl group (the lower alkyl group is a C1 to C6 lower alkylthio group). Group or C1-C6 lower alkylsulfonyl group may be substituted), C3-C6 lower alkenyl group, C3-C6 lower alkynyl group, phenylpropargyl group (the phenyl group is a halogen atom, C1-C6
A lower alkyl group or a C1 to C6 lower alkoxy group may be substituted) or a benzyl group.

The "leaving group" in the definition of X ¹ and X ² is not particularly limited as long as it is a group which usually leaves as a nucleophilic residue, but is preferably a chlorine atom, a bromine atom or an iodine atom. And halogen groups such as methane sulfonate and p-toluene sulfonate; sulfate groups such as methyl sulfate and ethyl sulfate; and phosphate groups such as dimethyl phosphate and diethyl phosphate.

In step A-1, aminophenol (II) is used.
Is etherified with a compound (III) to produce an aminophenol derivative (Ia) of the formula (I) in which R ² in the general formula (I) is a hydrogen atom.

The reaction is carried out in the presence of a base.

The base used is not particularly limited as long as it is a base having a strength that preferentially desorbs the protons of the phenols, but preferably an alkali metal such as sodium hydroxide or potassium hydroxide. Hydroxides; Alkali metal carbonates such as sodium carbonate and potassium carbonate; Metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide; Alkali metal hydrides such as sodium hydride and potassium hydride Aliphatic tertiary amines such as triethylamine, tri-n-butylamine, 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. You can get it.

The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent, but preferably water; methanol, ethanol, t-
Alcohols such as butanol; Ketones such as acetone, methyl isobutyl ketone; Nitriles such as acetonitrile; Esters such as ethyl acetate; Ethers such as diethyl ether, tetrahydrofuran, dioxane; Methylene chloride, Halogenated hydrocarbons such as chloroform and dichloroethane; aromatic hydrocarbons such as toluene; amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethylsulfoxide.

The reaction temperature is usually -70 ° C to 200 ° C, preferably -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,
It is normally 5 minutes to 24 hours, preferably 30 minutes to 5 hours
Time.

In step A-2, the nitrogen atom of the acylamino group of the compound (Ia) produced in step A-1 is alkylated, alkenylated, alkynylated, phenylpropargylated or benzylated to give a compound of the general formula It is a step of producing an aminophenol derivative (Ib) in which R ² in (I) is other than a hydrogen atom.

The reaction is carried out in the presence of a base.

The base used is not particularly limited as long as it is a base having a strength capable of desorbing a proton of an acylamino group, but is preferably sodium methoxide, sodium ethoxide or potassium t-butoxide. Metal alkoxides; alkali metal hydrides such as sodium hydride and potassium hydride; organometallic bases such as n-butyllithium, s-butyllithium, lithium diisopropylamide, sodium bistrimethylsilylamide, lithium bistrimethylsilylamide Can be mentioned.

The reaction solvent is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent, but alcohols such as methanol, ethanol and t-butanol; diethyl ether, Ethers such as tetrahydrofuran; dimethylformamide,
Amides such as dimethylacetamide; sulfoxides such as dimethyl sulfoxide.

The reaction temperature is usually -90 ° C to 150 ° C, preferably -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. In the compound (Ib), R ² is a phenylpropargyl group (the phenyl group is a halogen atom, C
1 to C6 lower alkyl group or C1 to C6 lower alkoxy group), R ⁴ of the compound (III) in the step A-1 above is a hydrogen atom and A is-. Using two or more equivalents of a compound of C≡C-
Step A-2 can also be carried out by reacting with 2 equivalents or more of a base.

The base used in this case is A-1
There is no particular limitation as long as it is a base having a strength capable of desorbing a phenol proton and an acylamino proton of the starting material (II) of the step, but preferably, such as sodium methoxide, sodium ethoxide, potassium t-butoxide. Metal alkoxides; alkali metal hydrides such as sodium hydride and potassium hydride; organometallic bases such as n-butyllithium, s-butyllithium, lithium diisopropylamide, sodium bistrimethylsilylamide, lithium bistrimethylsilylamide Can be mentioned.

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

The aminophenol derivative (Ia) can also be produced by the method (method B) shown below.

(Method B)

[0075]

Embedded image

During the above steps, R ¹ , R ³ , R ⁴ , R ⁵ ,
A, X ¹ , m and n have the same meanings as described above, and X ³ represents a leaving group.

The "leaving group" in the definition of X ³ is not particularly limited as long as it is a group which usually leaves as a nucleophilic residue.
Preferably, a halogen atom such as chlorine atom or bromine atom;
It is an acyloxy group represented by the formula "OCOR ¹ " (R ¹ has the same meaning as described above).

The step B-1 is a step for producing the compound (VI) by etherifying the nitrophenol compound (V) with the compound (III).

This step is carried out in the presence of a base, and A-1
It can be performed according to the process.

The step B-2 is a step for producing the aniline compound (VII) by reducing the nitro compound (VI) produced in the step B-1.

This step is carried out 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, but tin chloride is preferably used. There may be mentioned various transition metal halides, transition metal sulfates such as iron sulfate, and metals such as iron.

These reducing agents are used in the presence of acids such as hydrochloric acid and acetic acid. If necessary, it is further carried out in the presence of a solvent miscible with water for dissolving the nitro compound (VI).

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

The reaction temperature is generally -50 ° C to 200 ° C, preferably 0 ° C to 100 ° C. The reaction time varies depending mainly on the reaction temperature, the starting compound, the reaction reagent and the type of solvent used, but is usually 5 minutes to 24 hours, and preferably 30 minutes to 6 hours. Step B-3 is a step of producing compound (Ia) from aniline compound (VII) by acylating compound (VIII).

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

The base to be used is not particularly limited as long as it is used as a base in a usual reaction, but preferably alkali metal hydroxide such as sodium hydroxide and potassium hydroxide; carbonic acid. Alkali metal carbonates such as sodium and potassium carbonate; sodium hydride,
Alkali metal hydrides such as potassium hydride; Aliphatic tertiary amines such as triethylamine, tri-n-butylamine, 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; n-butyllithium, Mention may be made of organometallic bases such as s-butyllithium, lithium diisopropylamide, sodium bistrimethylsilylamide, lithium bistrimethylsilylamide.

The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent, but preferably water; methanol, ethanol, t-
Alcohols such as butanol; Ketones such as acetone, methyl isobutyl ketone; Nitriles such as acetonitrile; Esters such as ethyl acetate; Ethers such as diethyl ether, tetrahydrofuran, dioxane; Methylene chloride, Examples thereof include halogenated hydrocarbons such as chloroform and dichloroethane; aromatic hydrocarbons such as toluene and xylene.

The reaction temperature is usually -90 ° C to 200 ° C, preferably -50 ° C to 150 ° C. The reaction time varies depending mainly on the reaction temperature, the starting compound, the reaction reagent and the type of solvent used, but is usually 5 minutes to 24 hours, and preferably 15 minutes to 6 hours.

The method for producing a compound as a raw material of the above Method A or Method B will be described below.

The compound (I
I) is produced by the following method.

[0092]

[Chemical 15]

[In the formula, R ¹ , R ³ and n have the same meanings as described above. ] Phenol compound (IX) (this phenolic hydroxyl group may be carbonated in some cases) is nitrated by a conventional method such as a method using a mixed acid of concentrated sulfuric acid-concentrated nitric acid or a method using potassium nitrate, 4-nitrophenol compound (X) in which 4-position is nitrated
To manufacture. The nitro group is reduced according to a conventional method such as hydrogenation in the presence of concentrated Pd-C catalyst, stannous chloride in the presence of concentrated hydrochloric acid, and stannous chloride in acetic acid to reduce the phenol 4 A position-aminated 4-aminophenol compound (XI) is produced. Compound (X
I) is represented by the formula R ¹ COX ⁴ (R ¹ is as defined above,
X ⁴ represents a halogen atom. ), Various acyl halides are esterified in a conventional manner to give N, O
A diacylaminophenol compound (XII) is prepared. This compound (XII) is hydrolyzed in the presence of an alkali such as sodium hydrogen carbonate or sodium hydroxide to produce a compound (II) which is a raw material of step A-1.

The compound (III), which is the other raw material in step A-1 and the raw material in step B-1, is produced by the following method.

[0095]

Embedded image

[Wherein R ⁵ , A, m and X ¹ are as defined above, R ^4a is a C1 to C6 lower alkyl group,
X ⁵ represents a halogen atom. The compound (XIII) produced by the method described below is reduced by a conventional method using a reducing agent such as lithium aluminum hydride or sodium borohydride to produce a primary alcohol (XIV). This compound (XI
V) is oxidized according to the method described in J. Chem. Soc. (C) 2173, (1969) to produce an aldehyde (XV), which is an alkyl magnesium represented by the formula R ^4a MgX ^5. Compound (XVI) is produced by alkylation using a halide compound according to a conventional method.

Compound (XIV) thus obtained
The compound (III), which is a raw material in the steps A-1 and B-1, is produced by leaving the hydroxyl groups of (XVI) and (XVI) in a leaving group according to a conventional method.

The compound (XIII) is produced by the following production methods (1) to (3).

[0099]

[Chemical 17]

[Wherein R ⁵ and m have the same meanings as described above,
R ^6a represents a hydrogen atom, a fluorine atom, a chlorine atom or a C1-6 lower alkyl group, and R ^6b represents a bromine atom or an iodine atom. ], The compound (XVII) produced according to the method described in J. Org. Chem. 55 , (15) 4639 (1990) is treated with SY
According to the method described in NLETT 517, (1991), the compound (XV
III) is a step of producing a compound (XIIIa) in which A is represented by the formula —C (R ^6a ) ═CH— among the compounds (XIII).

In the step of, the compound (XIX) was treated with SYNLET
According to the method described in T 497, (1987), a compound (XX) is produced by reacting with a bromine molecule or an iodine molecule, and the compound (XVIII) is reacted with the compound (XII).
In step I), A is a step of producing a compound (XIIIb) represented by the formula —C (R ^6b ) ═CH—.

In the step (1), the compound (XIIIb-1) of the compound (XIIIb) produced by the method (1) is treated with a base such as lithium trimethylsilylamine according to a conventional method using the compound (XIIIb-1) in which R ^6b is an iodine atom as a starting material. Thus, in the compound (XIII), A is the formula-C.
This is a step of producing a compound (XIIIc) represented by ≡C-.

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, or if insoluble matter is removed 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 is mixed with a carrier and, if necessary, other auxiliary agents, and has a formulation form usually used as a herbicide such as powder, coarse powder, granule, granule, wettable powder,
It is used by preparing it as an aqueous solvent, an emulsion, a liquid agent and the like. The carrier as used herein refers to a synthetic or natural inorganic or organic substance that is mixed with a herbicide to help reach the plant of the active ingredient compound or to facilitate storage, transportation or handling of the active ingredient. means.

Examples of suitable solid carriers include clays represented by kaolinite group, montmorillonite group, attapulgite group, talc, mica, pyrophyllite, pumice, vermiculite, gypsum, dolomite, diatomaceous earth, magnesium. Lime, phosphorus lime, zeolite, silicic acid anhydride, synthetic calcium silicate, kaolin, bentonite,
Inorganic substances such as calcium carbonate, soybean flour, tobacco powder, walnut flour, wheat flour, wood flour, starch, vegetable organic substances such as crystalline cellulose, coumarone resin, petroleum resin, alkyd resin, polyvinyl chloride, polyalkylene glycol, ketone Examples thereof include synthetic or natural polymer compounds such as resins, ester gums, copal gums, dammal gums, waxes such as carnauba wax, paraffin wax, and beeswax, and 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 and chlorotoluene, ethers such as dioxane and tetrahydrofuran, acetone, methyl ethyl ketone,
Ketones such as diisobutyl ketone, cyclohexanone, acetophenone and isophorone, ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate, dibutyl maleate, esters such as diethyl succinate, methanol, n-hexanol, ethylene glycol, diethylene glycol, cyclo Alcohols such as hexanol and benzyl alcohol, ethylene glycol ethyl ether, ethylene glycol phenyl ether, diethylene glycol ethyl ether,
Examples thereof include ether alcohols such as diethylene glycol butyl ether, polar solvents such as dimethylformamide and dimethylsulfoxide, and water.

Surfactants used for the purpose of emulsification, dispersion, wetting, spreading, binding, control of disintegration, stabilization of active ingredient, improvement of fluidity, rust prevention, acceleration of absorption into plants, etc. It may be nonionic.

Suitable nonionic surfactants include, for example, sucrose esters of fatty acids, ethylene oxide polymerization adducts of higher aliphatic alcohols such as lauryl alcohol, stearyl alcohol and oleyl alcohol, and alkylphenols such as isooctylphenol and nonylphenol. Ethylene oxide polymerization adducts, butyl naphthol, octyl naphthol and other alkyl naphthol ethylene oxide polymerization adducts, palmitic acid, stearic acid, oleic acid and other higher fatty acid ethylene polymerization adducts, stearyl phosphate dilauryl phosphate and other mono- or dialkyls Ethylene oxide polymerization adducts of phosphoric acid, ethylene oxide polymerization adducts of higher aliphatic amines such as dodecylamine and stearic acid amide, higher fatty acid esters of polyhydric alcohols such as sorbitan, and ethylene oxide thereof. Copolymers of emissions polymerization adducts and ethylene oxide and propylene oxide can be cited.

Suitable anionic surfactants include, for example, sodium lauryl sulfate, alkyl sulfate ester salts such as oleyl alcohol sulfate ester amine salt, fatty acid salts such as sodium sulfosuccinate dioctyl ester, sodium oleate and sodium stearate. ,
Examples thereof include alkyl aryl sulfonates such as sodium isopropyl naphthalene sulfonate, sodium methylene bis naphthalene sulfonate, sodium lignin sulfonate, and sodium dodecylbenzene sulfonate.

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

Further, the herbicide of the present invention may contain other ingredients such as gelatin, gum arabic, casein, albumin, glue, sodium alginate, polyvinyl alcohol, for the purpose of improving the properties of the preparation and enhancing the biological effect. Carboxymethyl cellulose, methyl cellulose,
It may also contain a polymer compound such as hydroxymethyl cellulose, a sodium polyphosphate, a thixotropic agent such as bentonite, and other auxiliary agents.

The above-mentioned carrier and various auxiliary agents are appropriately used alone or in combination depending on the purpose in consideration of the application situation of the dosage form of the preparation.

Dusts usually contain 2 to 10 parts by weight of the active ingredient compound, the remainder being a solid carrier.

The wettable powder usually contains the active ingredient in an amount of 10 to 80 parts by weight, and the balance is a solid carrier and a dispersion wetting agent, and if necessary, a protective colloid agent, a thixotropic agent, an antifoaming agent and the like are added.

Granules usually contain 0.1 to 10 parts by weight of the active ingredient compound, and the balance is mostly 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, contains about 5 to 20 parts by weight of the emulsion, and the balance is a liquid carrier, and a rust preventive agent is added if necessary. .

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

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

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

Examples and formulation examples of the herbicide of the present invention are shown below and specifically described, but the present invention is not limited thereto.

[0121]

【Example】

[0122]

Example 1 O-phenylpropargyl-4-acetamidophenol (Compound No. 1.1) 0.85 g of 4-acetamidophenol was dissolved in 10 ml of dimethylformamide (DMF), and then 60% sodium hydride was added. 25 g was added. Next, 3 ml of a DMF solution containing 0.85 g of phenylpropargyl chloride was added, and the mixture was stirred at room temperature for 6 hours. After diluting with ethyl acetate, it was washed with water and dried over sodium sulfate. After the solvent was distilled off, the obtained crude crystals were recrystallized from a mixed solvent of isopropyl ether and methylene chloride to give the title compound having a melting point of 135 to 139 ° C.
12 g (yield 75%) was obtained.

Nuclear magnetic resonance spectrum (NMR) (200MH
z, CDCl ₃ ) δ: 7.12 (1H, br.s), 7.45-6.95 (9H, m), 4.89
(2H, s), 2.16 (3H, s).

[0124]

Example 2 O -Phenylpropargyl-4-butanamidephenol (Compound No. 1.3) (1) O-phenylpropargyl-4-nitrophenol
After dissolving Le 4-nitrophenol 5.00g dimethylformamide 100 ml, cooled in an ice-water bath, sodium hydride (60%) 1.58 g was added and after stirring for 10 min, phenyl propargyl chloride 5.19ml added The mixture was stirred at the same temperature for 1 hour. Further, the mixture was stirred at room temperature for 1 hour and then heated and stirred at 70 ° C. After allowing to cool, water was added and the mixture was extracted with ethyl acetate. Extract the solution with sodium bicarbonate water, 1N
-Washed with hydrochloric acid, water and saturated saline, dried over sodium sulfate, distilled off the solvent and purified by silica gel column chromatography (eluting solvent hexane: ethyl acetate = 20: 1) to give a melting point of 71-72 ° C. Having the title compound 5.70
g (63% yield) was obtained.

NMR (200 MHz, CDCl ₃ ) δ: 8.25 (2
H, br. d, J = 9.2 Hz), 7.48-7.3
8 (2H, br.s), 7.38-7.27 (3H,
br. s), 7.12 (2H, br.d, J = 9.3.
Hz), 5.03 (2H, s). (2) O-phenylpropargyl-4-aminopheno
After dissolving Le above the O- phenyl propargyl-4-nitrophenol 5.46g manufactured by the method of (1) to ethyl alcohol 55 ml, cooled in an ice-water bath, concentrated hydrochloric acid 40ml
Was gently added, then 10.22 g of stannous chloride was added little by little, and the mixture was stirred at the same temperature for 5 minutes, and then warmed to room temperature.
Stirred for hours. After heating and stirring at 70 ° C. for 3 hours, the mixture was allowed to cool to room temperature. Then, 10% sodium hydroxide aqueous solution was gradually added to the reaction solution until pH became 10,
It was extracted with ethyl acetate. After washing with water and drying over sodium sulfate, the solvent was evaporated and the residue was purified by silica gel column chromatography (elution solvent hexane: ethyl acetate = 3: 1) to give 3.14 g (yield 65%) of the title compound as an oil. Obtained.

NMR (200 MHz, CDCl ₃ ) δ:
7.47-7.41 (2H, m), 7.36-7.25 (3H, m), 6.90 (2H, br.d, J =
9.0Hz), 6.67 (2H, br.d, J = 8.8Hz), 4.83 (2H, s), 3.46 (2
H, br.s). (3) O-phenylpropargyl-4-butanamide
Knoll After dissolving 109.1 mg of O-phenylpropargyl-4-aminophenol prepared by the above method (2) in 2.2 ml of methylene chloride, it was cooled in an ice-water bath and 0.08 ml of triethylamine and 0.06 ml of butyryl chloride were dissolved. Was added and stirred for 5 minutes, and then stirred at room temperature for 1 hour. Water was added to the reaction solution, which was extracted with methylene chloride. After washing with water, washing with saturated saline, drying over sodium sulfate, evaporation of the solvent, silica gel column chromatography (elution solvent
Purified with hexane: ethyl acetate = 3: 1), mp 107
135.8 mg of the title compound having a .about.110 ° C. (yield 9
5%).

NMR (200 MHz, CDCl ₃ ) δ: 7.49-7.36 (4
H, m), 7.35-7.27 (3H, m), 7.07-6.95 (3H, br.m), 4.89 (2
H, s), 2.33 (2H, t, J = 7.2Hz), 1.76 (2H, q, J = 7.6Hz).

[0128]

Example 3 O-Cinnamoyl-4-acetamidophenol (Compound No. 6.1) In a mixed solution of 15 ml of acetonitrile and 5 ml of DMF, 1.44 g of cinnamoyl bromide, 1.0 g of acetamide phenol and 0 potassium t-butoxide were added. 0.89 g was added and the mixture was stirred at room temperature for 1 hour and at 60 ° C. for 1 hour. After cooling, it was diluted with ethyl acetate, washed with water and dried over sodium sulfate. After evaporating the solvent, the residue was purified by silica gel column chromatography (eluting solvent hexane: ethyl acetate = 3: 1) to give the title compound 1.14 having a melting point of 170-172 ° C.
g (yield 65%) was obtained.

NMR (200 MHz, CDCl ₃ ) δ: 7.42-7.25 (7
H, m), 7.07 (1H, br.s), 6.92 (2H, d, J = 8.8Hz), 6.73 (2H,
d, J = 16.2Hz), 6.40 (2H, dt, J = 16.2Hz, 5.8Hz), 4.68 (2H,
d, J = 5.8Hz), 2.16 (3H, s).

[0130]

Example 4 O- (trans-3-phenyl-2-chloro-2-pro
Penenyl) -4-acetamidophenol (Compound No. 7.
1) After dissolving 80.2 mg of 4-acetamidophenol in 1 ml of dimethylformamide, it was cooled in an ice-water bath, 25.5 mg of sodium hydride (60%) was added, and the mixture was mixed at 10
After stirring for 1 minute, a solution of 99.2 mg of trans-β-chloro-cinnamyl chloride dissolved in 1 ml of dimethylformamide was added at the same temperature, and the mixture was warmed to room temperature and stirred for 2 hours. Water was added to the reaction solution and extracted with ethyl acetate,
After washing with water, the extract was washed with saturated saline and dried over sodium sulfate. After distilling off the solvent, the title compound 11 having a melting point of 102 to 104 ° C. was purified by silica gel column chromatography (elution solvent hexane: ethyl acetate = 1: 1).
0.0 mg (yield 69%) was obtained.

NMR (270 MHz, CDCl ₃ ) δ: 7.62-7.40 (7
H, m), 7.24-7.15 (2H, m), 7.02 (2H, br.d, J = 9.3Hz), 4.92
(2H, s), 2.34 (3H, s).

[0132]

Example 5 O- (3-phenyl-2-methyl-2-propynyl)-
4 -acetamidophenol (Compound No. 4.1) After dissolving 148.7 mg of 4-acetamidophenol in 2 ml of dimethylformamide, it was cooled in an ice-water bath, 43.3 mg of sodium hydride (60%) was added, and the same temperature was added. After stirring for 10 minutes at room temperature, a solution of 264.7 mg of 1-phenyl-3-methanesulfonyloxy-1-butyne in 2 ml of dimethylformamide was added at the same temperature,
After further stirring for 5 minutes, the mixture was stirred at room temperature for 3 hours. Water was added to the reaction solution, extracted with diethyl ether, washed with water, and dried over sodium sulfate. After the solvent was distilled off, the residue was purified by silica gel column chromatography (eluting solvent hexane: ethyl acetate = 1: 1) to obtain 142.7 mg (yield 52%) of the title compound having a melting point of 124 to 128 ° C.

NMR (200 MHz, CDCl ₃ ) δ: 7.45-7.24 (6
H, m), 7.08-6.98 (3H, m), 5.05 (1H, q, J = 6.3Hz), 2.16 (3
H, s), 1.73 (3H, d, J = 6.6Hz).

[0134]

[Formulation example]

[0135]

[Formulation Example 1] (Wettable powder) 25% compound No. 1.1, sodium dodecylbenzenesulfonate 2.5%, calcium ligninsulfonate 2.5% and diatomaceous earth 70% are well pulverized and mixed to obtain a wettable powder. Got

[0136]

[Formulation Example 2] (Emulsion) No. 3.3 compound 30%, dodecylbenzenesulfonic acid calcium salt 2.68%, polyoxyethylene alkyl ether 4.92%, polyoxyethylene nonylphenyl ether phosphate calcium salt 0.4% and xylene. 62% was mixed well to obtain an emulsion.

[0137]

[Formulation Example 3] (Granule) No. 5.5 compound 5%, white carbon 1%,
Lignin sulfonate calcium salt 5%, bentonite 2
0% and 69% of clay were well pulverized and mixed, water was added and well kneaded, and then granulated and dried to obtain granules.

[0138]

[Formulation Example 4] (Hydrated granules) No. 5.10 compound 80%, special polycarboxylic acid polymer sodium salt 1.25%, water 3.75%, dodecylbenzene sulfonic acid sodium salt 3%, dextrin 7% and oxidation Titanium 5% is mixed, then ground in an air mill and added to a rotary mixer or fluid bed mixer,
It was granulated by spraying with water. Mostly 1.0-0.15
When the size became mm, the granules were taken out, dried and sieved.
Oversize material is crushed to 1.0-0.15mm
Granules of

[0139]

[Formulation Example 5] (Aqueous suspension) Compound No. 5.34 (25 parts), sodium dioctylsulfosuccinate (0.7 parts), propylene glycol (0.15 parts), ligninsulfonic acid calcium salt (10)
Parts, 44.15 parts of water and 10 parts of propylene glycol were milled together in a ball mill, sand mill or roller mill until the solid particles were reduced to a diameter of 5 microns or less. To 90 parts of this pulverized slurry, 0.05% (W /
W) 10 parts of xanthan gum aqueous solution was added and mixed to obtain an aqueous suspension.

[0140]

The compound of the present invention has a herbicidal action and can be used as a herbicide. For example, paddy field weeds such as Taenia cinerea, Hymetainuvier and Keiubie, which are strong weeds in paddy fields, can be strongly controlled by treating the flooded soil in the paddy fields before or after germination of the weeds.

On the other hand, the selectivity for paddy rice is high,
Transplanted rice has the advantage that it can be applied to a wide range of applications because it does not suffer chemical damage.

Next, the effects will be concretely shown by giving examples of biological tests.

[0143]

[Test Example 1] Pre-germination treatment of paddy field weeds A 100 cm ² pot was filled with paddy soil, and seeds of Taenia japonica that had been awakened were mixed into the surface layer of 1 cm. In addition, seedlings of paddy rice at the two-leaf stage were transplanted into a submerged state and grown in a greenhouse. Three days later, the wettable powder prepared according to Formulation Example 1 was used to treat the submerged soil with a predetermined dose, and 21 days later, an investigation was conducted according to the following criteria. The results are shown in Table 8. (Judgment Criteria) 0: Growth inhibition rate 0-10% 1: Growth inhibition rate 11-30% 2: Growth inhibition rate 31-50% 3: Growth inhibition rate 51-70% 4: Growth inhibition rate 71-90% 5 : Growth inhibition rate 91-100%

[0144]

[Test Example 2] 1.5 leaf stage treatment of Tainubie In the same manner as in Test Example 1, a prescribed dose was submerged in the 1.5 leaf stage of Tainubie using a wettable powder prepared according to Formulation Example 1. The soil was treated and surveyed 21 days later. The results are shown in Table 8 (determination criteria are the same as in Test Example 1).

[0145]

[Table 8] ──────────────────────────────────── Compound number Drug amount (g / a) Paddy field Weed germination pre-treatment Tainubie 1.5 Leaf stage treatment Tainubier Paddy rice Tainubie Paddy rice ──────────────────────────────────── --1.1 20 5 0 5 0 1.1 1.1 10 5 0 5 0 0 1.1 5 5 5 0 5 0 1.6 1.6 20 5 0 5 5 0 1.6 1.6 10 5 0 5 0 0 1.6 5 5 0 5 5 0 1 .9 20 5 0 5 0 0 2.11 20 5 0 5 5 0 3.3 3.3 20 5 0 5 0 3.5 3.5 20 5 0 5 5 0 3.10 20 5 0 5 0 0 4.2 20 5 0 4 0 5.2 20 5 0 4 0 5.3 5.3 20 5 5 0 4 0 5.4 5.4 20 5 0 5 5 0 5.4 5.4 10 5 0 5 5 0 5 4 5 5 0 5 5 0 5 5 20 5 0 5 5 0 5 5 5 10 5 0 5 0 5.5 5 5 0 5 0 5 5.6 20 5 5 0 5 0 5.6 6 10 5 0 5 5 0 5.6 5 5 5 0 5 0 5.8 20 20 5 0 5 5 0 5.8 10 5 0 5 5 0 5.8 5 5 0 5 0 5.9 20 5 5 0 5 0 5.9 10 5 5 0 5 0 5.9 5 5 5 0 4 0 5.10 20 5 0 5 5 0 5.10 10 5 0 5 5 0 5.10 5 5 5 4 0 5.19 20 5 0 4 0 0 5.21 20 5 0 5 5 0 5.32 20 5 0 5 5 0 5.32 10 5 0 4 0 5 5.32 5 4 0 4 0 5 5.34 20 5 0 5 5 0 5 0.34 10 5 0 5 0 5.34 5 5 0 4 0 5.36 20 5 0 5 5 0 5.43 20 5 0 4 0 5.44 20 5 5 0 4 0 5.46 20 5 0 4 0 6.1 20 5 0 3 0 6.6 6 20 5 5 0 5 0 6.6 6 10 5 0 5 0 6 6 6 5 5 5 0 5 0 6.7 20 5 0 4 6.8 20 5 5 0 5 6.17 20 5 0 4 0 6.30 20 5 0 5 5 0 7.1 20 4 0 5 0 7 7.2 20 4 4 0 4 0 7.15 20 5 0 5 5 0 7. 22 20 4 0 3 0 7.24 20 4 0 3 0 7.25 20 5 0 4 0 ───────────────────────────── ──────── Comparative Compound A 20 1 0 2 0 Comparative Compound A 10 0 0 0 0 Comparative Compound A 5 0 0 0 0 Comparative Compound B 20 0 0 0 0 Comparative Compound B 10 0 0 0 0 Comparative Compound B 5 0 0 0 0 ───────────────────────────────────── In the above table, Comparative Compound A is USP 4,289,903
Comparative compound B is a compound represented by the following formula described in JP-A-59-193810.

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 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toyokuni Honma 1041 Yasu, Yasu-cho, Yasu-gun, Shiga Sankyo Stock Company

Claims (5)

[Claims] 1. A compound represented by the following general formula (I): [In the formula, R ¹ is a C1 to C6 lower alkyl group (the lower alkyl group may be substituted with a halogen atom)
R ² represents a hydrogen atom, a C1 to C6 lower alkyl group (the lower alkyl group may be substituted with a C1 to C6 lower alkylthio group or a C1 to C6 lower alkylsulfonyl group), C3 to C6 lower Alkenyl group, C
3 to C6 lower alkynyl group, phenylpropargyl group (the phenyl group may be substituted with a halogen atom, C1 to C6 lower alkyl group or C1 to C6 lower alkoxy group) or benzyl group, and R ³ is C1
To C6 lower alkyl group, C1 to C6 lower alkoxy group or a halogen atom, R ⁴ represents a hydrogen atom or C1 to C
6 lower alkyl group, R ⁵ is a C1 to C6 lower alkyl group, a C1 to C6 lower alkoxy group, a phenoxy group,
A halogen atom or a trifluoromethyl group is shown, and A is
A group represented by the formula -C≡C- or a formula -C (R ⁶ ) = CH-
(R ⁶ represents a hydrogen atom, a C1 to C6 lower alkyl group or a halogen atom), and n is 0 or 1.
To 4 (provided that n is 2 to 4, each R ³ may be the same or different), and m is 0.
Or an integer of 1 to 5 (provided that when m is 2 to 5, each R ⁵ may be the same or different). ] The aminophenol derivative represented by. 2. The following general formula (I): [In the formula, R ¹ is a C1 to C4 lower alkyl group (the lower alkyl group may be substituted with a halogen atom)
Are shown, R ² is a hydrogen atom, C1 -C4 lower alkyl group, C3-C5 lower alkenyl group, C3-C5 lower alkynyl group, a phenyl propargyl group (said phenyl group, a halogen atom, C1 -C4 lower alkyl group or C1
To C3 may be substituted with a lower alkoxy group)
Or a benzyl group, R ³ represents a C1 to C4 lower alkyl group, a C1 to C3 lower alkoxy group or a halogen atom, R ⁴ represents a hydrogen atom or a C1 to C4 lower alkyl group, and R ⁵ represents C1 To C4 lower alkyl group, C1 to C
3 is a lower alkoxy group, a phenoxy group or a halogen atom, and A is a group represented by the formula —C≡C— or a formula —C
A group represented by (R ⁶ ) ═CH— (R ⁶ is a hydrogen atom,
C1 to C4 is a lower alkyl group or a halogen atom, and n is 0 or an integer of 1 to 4 (where n is 2).
In the case of 4 to 4, each R ³ may be the same or different), m is 0 or an integer of 1 to 5 (provided that
When m is 2 to 5, each R ⁵ may be the same or different). ] The aminophenol derivative represented by. 3. The following general formula (I): [In the formula, R ¹ represents a methyl group (the methyl group may be substituted with a fluorine atom or a chlorine atom), and R ²
Represents a hydrogen atom or a phenylpropargyl group (the phenyl group may be substituted with a fluorine atom, a chlorine atom or a methoxy group), R ³ represents a methyl group or a chlorine atom, and R ⁴ represents hydrogen. An atom, R ⁵ represents a methyl group, a methoxy group, a fluorine atom or a chlorine atom, and A represents
A group represented by the formula -C≡C- or a formula -C (R ⁶ ) = CH
Represents a group represented by- (R ⁶ represents a hydrogen atom or a chlorine atom), n represents 0, 1 or 2 (provided that when n is 2, each R ³ is the same or different) And m is 0, 1 or 2 (provided that when m is 2, each R ⁵ may be the same or different). ] The aminophenol derivative represented by. 4. The following general formula (I): [In the formula, R ¹ represents a methyl group or a fluoromethyl group, R ² represents a hydrogen atom, R ³ represents a methyl group, R ⁴ represents a hydrogen atom, and R ⁵ represents a methoxy group. , A fluorine atom or a chlorine atom, A represents a group represented by the formula —C≡C—, n represents 0, 1 or 2 (provided that when n is 2, each R ³ is the same). Or m may be 0, 1 or 2 (provided that when m is 2, each R ⁵ may be the same or different). ] The aminophenol derivative represented by. 5. A herbicide containing the aminophenol derivative according to any one of claims 1 to 4 as an active ingredient.