WO2001079199A1 - Acetylene derivatives and herbicides containing the same - Google Patents

Abstract

Acetylene derivatives represented by the general formula (I); and herbicides containing the derivatives and/or salts thereof as the active ingredient. In said formula R?1 to R6, X1¿, Y, Z and q are each as defined in the description. The acetylene derivatives and the herbicides do not cause chemical damage to upland crops such as corn, and can control a wide variety of upland weeds even in a low dosage.

Description

 Description Acetylene derivatives and herbicides using the same

 The present invention relates to a novel acetylene derivative and a herbicide using the same. More specifically, the present invention provides an acetylene derivative capable of controlling a wide range of field weeds at a low dose without causing phytotoxicity to field-cultivated crops such as corn, and an acetylene derivative containing the acetylene derivative as an active ingredient. It relates to herbicides. Background art

 Herbicides are extremely important drugs for labor saving in weed control and for improving the productivity of agricultural and horticultural crops.Therefore, research and development of herbicides has been actively carried out for many years, and a wide variety of chemicals are currently in practical use. ing. Therefore, even today, the development of new drugs with even more excellent herbicidal properties, especially those that can control only the target weeds at low doses without causing phytotoxicity to cultivated crops, has been developed. It is desired.

 Conventionally, at the time of cultivation of corn and the like, atrazine, a triazine herbicide,

(atrazine) and the acid-based herbicides alaclor (a1 achlor) and metolachlor have been used, but atrazine has low activity against grass weeds. Conversely, it has low activity against broadleaf weeds. Therefore, it is currently difficult to control gramineous and broadleaf weeds at once with a single agent. In addition, these herbicides require high doses and are not preferred on environmental issues.

 By the way, it is known that certain 4-benzoyl derivatives have herbicidal activity (JP-A-63-122672, JP-A-63-122673, JP-A-63-170365, JP-B-Hei-1-152759, Nos. 2-173 and 2-288866), and the currently marketed herbicides include pyrazolate represented by the following chemical formula:

^ pyrazolate) There is power S.

 However, although these 41-benzoyl derivatives have herbicidal activity, they are practically insufficient, and in particular, their herbicidal activity on grass weeds such as Nobie and Enokorogusa is extremely poor. In order to solve these disadvantages, a compound in which a thiochroman ring and a virazole ring are bonded has been applied for a patent (WO95 / 04054). Representative examples of the compounds described in this publication are shown below.

 Compared with the 4-benzoyl derivative, these chiochroman derivatives have a high herbicidal activity 1 ", but are not sufficient. Furthermore, their safety against corn is also insufficient.

 The present invention provides a novel compound capable of controlling a wide range of field weeds at a low dose without causing phytotoxicity to field cultivated crops such as corn under such circumstances, and a herbicide using the same. It is intended to provide an agent.

The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a pyrazole compound having a specific structure in which an acetylene group is introduced into the molecule can achieve the object. The present invention has been completed based on such findings. That is, the present invention provides a compound represented by the general formula (I):

 Where X is an oxygen atom, or

C '' N ~

 (However, when X represents an asymmetric group, the bond on the left is bonded to the benzene ring, and the bond on the right is bonded to the Y moiety.)

Represents a group represented by

Y is the formula

 (However, when Y represents a left-right asymmetric group, the bond on the left is bonded to the X part, and the bond on the right is bonded to the Z part.)

Represents a group represented by

z is an oxygen atom or formula

 40 R 40

 • N— S1 ~~ N ~ C

0 ₂

 (However, when z represents an asymmetric group, the bond on the left is bonded to the benzene ring, and the bond on the right is bonded to the Y moiety.)

Represents a group represented by

 However, the following general formula (V):

When the substituent represented by is bonded to the benzene ring at the meta position with respect to R ⁵ , Z is not 1 SO ₂ —.

で表される基である場合には、 Xが酸素原子及び式Y is the expression

When X is a group represented by the formula:

R ²⁶

— C = N——

It is not a group represented by

 Y is the expression

 π30

 it ix xx

 ~ N—— or —— C— N ~

R ²⁹

When Z is a group represented by the formula,

O— S— — S— 0

o ₂ 0 is not a group represented by _2.

 When Y represents an oxygen atom, X is represented by the formula

—

Wherein Z is a group represented by the formula

Represents a group represented by

 When Y represents a sulfur atom, is represented by the formula

R ⁷ R ²⁶ R ²⁷

 C— or one C = C

R ⁸

Wherein Z is a group represented by the formula

X ⁷ R ³⁵

 II I

 — C— or one c—

3 ⁶

Represents a group represented by Y is the expression

 , 28, 28

 .

 -C— O— or —— C— S——

 • In the case of a group represented by R29 ^ 29, X is an oxygen atom or a formula

R ⁷ OR 10

One C-One N-

Represents any of the groups represented by

 Five

 II

 ■ C- or -C—

 And a group represented by 36.

R ¹ is a hydrogen atom, a halogen atom, one or two oxygen atoms and / or sulfur atom may be interrupted, the alkyl group may ₆ chain have a halogen atom or c ₃ to c _s cyclic alkyl group or a C ₂ -C ₆ alkenyl group,, C ₂ to c ₆ Haroanorekeniru group, C ₂ -C ₆ Arukyuru group, Shiano group, a carboxyl group,

(C CA alkoxy) carbyl group, tri (.- dialkyl) silyl group, C i Cs alkylthio group, C ₆ -C ₆ alkyl sulfier group, C ₁ -C ₆ alkyl sulfonyl group, substituted or unsubstituted phenylthio Group, substituted or unsubstituted phenylsulfuryl group, substituted or unsubstituted phenylsulfonyl group, C ₁ -C ₆ anolexoxy group, substituted or unsubstituted phenoxy group, substituted or unsubstituted phenyl group

A sulfur or a substituted or unsubstituted 5- or 6-membered aromatic heterocyclic group, wherein the sulfur atom may be partially or completely oxidized by oxygen.

R ² is a hydrogen atom, a halogen atom, one or two oxygen atoms and no or sulfur May be interrupted by atom, also good Ci Cs chain optionally having a halogen atom Joa Kill group or C ₃ -C ₆ cyclic alkyl group or a C ₂ -C ₆ alkenyl group,, C ₂ -C ₆ Haloalkenyl group, C ₂ -C ₆ alkynyl group, cyano group, carboxyl group, (CC alkoxy) carbyl group, tri (C ₁ -C ₄ alkyl) silyl group, substituted or unsubstituted funil group, or substituted or unsubstituted A substituted 5- or 6-membered aromatic heterocyclic group, wherein the sulfur atom may be partially or completely oxidized by oxygen;

R ³ is a hydrogen atom, one or two oxygen atoms and Z or may be interrupted by a sulfur atom, also a halogen atom or may ₆ chain alkyl group which may have a is c ₃ to c ₆ cyclic alkyl or c ₂ to c ₆ alkenyl group,, c ₂ to c ₆ Haroa alkenyl group, a C ₂ -C ₆ Arukyuru group, the sulfur atom may be partially or completely oxidized by oxygen.

R ⁴ may be interrupted by a hydrogen atom, one or two oxygen atoms and / or sulfur atoms, and may have a halogen atom.Ci-C ₆ chain alkyl group, or C ₂ -C ₆ alkenyl group, C ₂ -C ₆ haloalkenyl group, a C ₂ -C ₆ alkynyl group, Shiano group, a carboxyl group or a - (Ji ~. alkoxy) force Rupoeru group, the sulfur atom to the oxygen It may be partially or completely oxidized.

R ⁵ is a hydrogen atom, a halogen atom, a nitro group, one or two oxygen atoms and Z or a sulfur atom may be interrupted by, or optionally C i to C ₆ chain which may have a halogen atom An alkyl group or a C ₃ -C ₆ cyclic alkyl group, or a propyloxyl group, a cyano group, a thiocyano group, a CiC alkoxyl group,. , Roarukokishiru group, (Ci C alkoxy) carbonyl group, a mercapto group, C ₁ -C ₄ alkylthio O group, C ~ 〇 ₄ alkylsulfinyl group, Ji-Ji alkylsulfonyl group, C ₂ -C ₆ Arukeyuru group, C ₂ -C ₆ haloalkenyl group or C ₂ -C ₆ alkynyl group, and the sulfur atom contained in the above-mentioned C ₆ -C ₆ chain alkyl group or C ₃ -C ₆ cyclic alkyl group is partially or completely depleted by oxygen. It may be oxidized.

R ⁶ is a halogen atom, a nitro group, one or two oxygen atoms and Z or a sulfur atom may be interrupted by, or optionally C ～〇 ₆ chain alkyl group which may have a halogen atom or a C _{3 to} C ₆ cyclic alkyl group, or carboxyl group, cyano group, thiocyano group, alkoxyl group, haloalkoxyl group, -C ₄ alkoxy) carboxy group, a mercapto group, Ci C alkylthio group, -C ₄ alkyl sulfide El group, C i~C ₄ alkylsulfonyl group, C ₂ ~ ₆ Al Keeru group, 〇 ₂ ～〇 ₆ haloalkenyl group, or a C ₂ -C ₆ alkynyl group, the

The sulfur atom contained in the C i -C ₆ chain alkyl group or the C ₃ -C ₆ cyclic alkyl group may be partially or completely oxidized by oxygen.

Xi X ⁷ represents an oxygen atom or a sulfur atom, respectively.

R ⁷ and R ⁸ may be each independently interrupted by a hydrogen atom, a halogen atom, a nitro group, one or two oxygen atoms and a Z or sulfur atom, and have a halogen atom. which may be C ~ C ₆ linear alkyl or C ₃ ~ C ₆ cycloalkyl group or a carboxyl group, Shiano group, Ci C alkoxyl group, Ci～C _¾ Roh, Roarukokishiru group, (C ₁ -C ₄ Alkoxy) alcohol group, C ₁ -C ₄ alkynolethio group, alkylsulfiel group, C alkylsulfonyl group, formula

-CHR ³⁷ NO ₂ , -CHR ³⁷ NR ¹³ R ¹⁴ , —CHR ³⁷ P (= 0) (OR ³⁸ ) ₂ , — NR ¹³ R ¹⁴ , — NR ³⁷ COR ³⁹ , —NR ³⁷ C0 ₂ R ³⁸ , — NR ³⁷ S0 ₂ R ³⁹ , — OCOR ³⁹ , -OC0 ₂ R ³⁷ , one OCONR ¹³ R ¹⁴ , one OCHR ³⁷ CN, — O CHR ³⁷ COR ³⁹ , _OCHR ³⁷ C0 ₂ R ³⁸ , — OC HR ³⁷ C ON R ¹³ R ¹⁴ , — S0 ₂ NR ¹³ R ¹⁴ , one OS 0 ₂ R ³⁹ , -0-N = CR ¹³ R ³⁷ , — P (= 0) (OR ³⁸ ) ₂ , one OP (= 0) (〇R ³⁸ ) ₂ a group represented by a substituted or unsubstituted phenylene group, or a substituted or unsubstituted 5-membered or 6-membered ring aromatic heterocyclic group indicates, the Ci Ce-chain alkyl group or C ₃ ~C sulfur atom contained in the _S cycloalkyl group may be partially or completely oxidized by oxygen.

R ⁹ is a hydrogen atom, C Cs alkyl group, C Ce haloalkyl group, - shows the S0 ₂ R ³⁹ - COR ³⁹ or.

R ¹⁰ may be interrupted by a hydrogen atom, one or two oxygen atoms and / or sulfur atoms, and may have a halogen atom. C _{1 to} C ₆ chain alkyl group or C ₃ to C ₆ cyclic alkyl group or a C ₂ -C ₆ alkenyl, - le group, C ₂ -C ₆ Haroa Rukeeru group, C ₂ -C ₆ alkynyl group or formula _{^{_COR 39,, -C0 2 R 37}} , -CH R 37 CN ^{, - CHR 37 COR 39, -} C HR 37 CO 2 R 38, -CHR ^ CONR 1 3 R 14, - CONR 13 R 14, - S_〇 a group represented by ₂ R ^39, the Ci Ce linear The sulfur atom contained in the alkyl group or C ₃ -C ₆ cyclic alkyl group is It may be partially or completely oxidized.

R ¹¹ and R ¹² are each independently a hydrogen atom, a nitro group, a carboxyl group, a cyano group, a di-alkyl group,. ~ 〇 represents a haloalkyl group, a (CC alkoxy) carbol group or COR ³⁹ .

R ¹³ represents a hydrogen atom, a Ci Cs alkyl group, a Ci Ca haloalkyl group, or a substituted or unsubstituted phenyl group.

R ¹⁴ represents a hydrogen atom, a halogen atom, a C i C alkyl group or a haloalkynole group.

R ¹⁵ ~R ^23, R ²⁶ and R ²⁷ are each a hydrogen atom, a halogen atom, Ci C alkyl group or.じ represents a mouth alkyl group.

R ²⁴ and R ²⁵ are each a hydrogen atom, a halogen atom, Ci Ca alkyl group, C i~C ₄ haloalkyl group, an alkoxyl group, Ji ~ JiヽRoanorekokishi group, a carboxyl group, (C ₁ -C ₄ alkoxy) Karuponiru group, Ci～C ₄ alkyl thio groups, C ～〇 ₄ alkylsulfinyl groups, C ~ C ₄ alkylsulfonyl - group, an amino group, a mono (Ci C alkyl) amino group or a di (Ci C alkyl) amino group Show.

R ^28, 1 ²⁹ and 1 ³¹ to 1 ³⁴ are each a hydrogen atom, a halogen atom, Ci C alkyl group or.じ represents a mouth alkyl group.

R ³⁵及Pi R ³⁶ are each independently a hydrogen atom, a halogen atom, Ci CT alkyl group, Ji-Ji, mouth alkyl group, C ₁ -C ₄ forces or R 3 ⁵ illustrates an alkoxyl group, R ³⁶ and The carbon atoms to which they are attached together form the formula

で表される基を形成してもよい。

May be formed.

R ³⁰ , R ³⁷ , R ³⁸ and R ⁴⁰ each represent a hydrogen atom or an alkyl group.

R ³⁹ represents a CiC alkyl group, 〇 to 〇, a loalkynole group or a substituted or unsubstituted phenyl group.

 n represents 0 or 1.

m, p and q each represent 0, 1 or 2, when p is 2, two R ²⁴ may be the same or different, and when q is 2, two R ⁶ are each other They may be the same or different. ] The acetylene derivative represented by these is provided. The present invention also provides a herbicide containing the acetylene derivative and / or a salt thereof as an active ingredient. Best mode for implementing efforts

 First, the acetylene derivative of the present invention will be described.

 The acetylene derivative of the present invention has the general formula (I)

It is a compound represented by these.

In the general formula (I), X is an oxygen atom or a formula

R ³

26

R ²⁶ R ²⁷ R'X. R 13 R ¹³ X ⁶

-C = C- —— C = N- ― C— Ν · -N— C-

Where X represents an asymmetric group, the bond on the left is bonded to the benzene ring, and the bond on the right is bonded to the Y moiety.

Y is the formula 33

R ²⁸ R ³⁰ R ²⁸ E ³¹ 8 R ³⁰ R ²⁸ R ³¹ R '

1 1 1 1 1 1 1 1 1

■ c— ~ N——-— c— -c— — c— -N—— ■ c— -c— -c

 1 3, 4

R ²⁹ R ²⁹ R ³² R ²⁹ E ²⁹ R ³² E '

Where Y represents an asymmetric group, the bond on the left is bonded to the X moiety, and the bond on the right is bonded to the Z moiety.

 On the other hand, Z is an oxygen atom, or the formula

Where Z represents an asymmetric group, the bond on the left is bonded to the benzene ring, and the bond on the right is bonded to the Y moiety.

 However, the following general formula (V):-

When the substituent represented by is bonded to the benzene ring at the meta position with respect to R ⁵ , Z is not 1 SO ₂ —.

 Y is the expression

-N—

When X is a group represented by the formula: R ²⁶

 -C = N——

It is not a group represented by

又は —— C— N ~ で表される基である場合には、 Zが式Y is the expression

Or —— C— N ~ when it is a group represented by

― 0― S― ― S― 0―

0 is not a ₂ 0 ₂ in a group represented by.

 When Y represents an oxygen atom, is represented by the formula

T.7 _π 26 τ, 27

 XV t Iv

 — C— or —— c = c—

R ⁸

And Z is a group represented by the formula

Represents a group represented by

When Y represents a sulfur atom, X is represented by the formula

Wherein Z is a group represented by the formula

X ⁷ R ³⁵

 II I

 — C— or one c—

_The group represented by _R 36 is shown.

Y is the expression

And Z represents a group represented by the formula

Represents a group represented by

R ¹ is a hydrogen atom, a halogen atom, one or two oxygen atoms and / or sulfur atom may be interrupted by, or optionally C i~C ₆ chain alkyl group which may have a halogen atom or a C ₃ ~ C ₆ cycloalkyl group or a C ₂ -C ₆ alkenyl, - le group, C ₂ to c ₆ haloalkenyl group, or c ₂ to c ₆ alkyl group, Shiano group, a carboxyl group, (Ci C alkoxy ) Karuponiru group, tri (Ji-Ji alkyl) silyl group, C Ce alkylthio group, C ₁ -C ₆ alkyl sulfide El group, C ₁ -C ₆ alkyl Rusuruhoniru group, a substituted or unsubstituted phenylene group, a heteroarylthio group, a substituted or unsubstituted Hue Nils sulfinyl group, a substituted or unsubstituted winter sulfonyl sulfonyl group, 〇 ~ C ₆ alkoxy group, a substituted or unsubstituted phenoxy group, a substituted or unsubstituted phenyl group or a substituted young properly, Indicates aromatic heterocyclic group having 5 or 6 membered unsubstituted, said sulfur atom may be partially or completely oxidized by oxygen. Here, the one where the sulfur atom is partially oxidized is a sulfoxide group (one so—), and the one where the sulfur atom is completely oxidized is a sulfone group (one so ₂ —). You. The same applies to the following description.

 When the above-mentioned phenyl group, phenylthio group, phenylsulfinyl group, phenylsulfonyl group, phenoxy group or aromatic heterocyclic group has a substituent, examples of the substituent include a halogen atom, a nitro group, Carboxyl group, cyano group,

C ₄ alkyl group, Ci-C, mouth alkyl group, Ci CA alkoxyl group, Ci C haloalkoxynole group, (.-dialkoxy) carboyl group, alkylthio group, CC AT norequils / refinyl group and C i- One or two groups selected from the group consisting of C ₄ alkynolesulfenol groups are preferred.

Among such R ¹ , preferred are a hydrogen atom, a halogen atom, a C ₆ -C ₆ alkyl group which may be interrupted by one or two oxygen atoms and / or sulfur atoms, and C i Ce haloalkyl group or a C ₃ -C ₆ cycloalkyl group, more can be mentioned tri (Ci C alkyl) silyl group, a (Ji-Ji alkoxy) carbonyl group, and Fueeru group, as more preferable, a hydrogen atom, halogen And a CiC alkyl group. Particularly preferred are a hydrogen atom, a methyl group and an ethyl group.

R ² is a hydrogen atom, a halogen atom, one or two oxygen atoms and / or sulfur atom may be interrupted by, also have good Ci Ce-chain alkyl group or a C ₃ be ~ a halogen atom C ₆ cyclic alkyl group, or C ₂ -C ₆ alkenyl group, C ₂ -C ₆ haloalkyl group, or C ₂ -C ₆ alkyl group, cyano group, carboxyl group, (C i C alkoxy) carboyl group, tri Alkyl) represents a silyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted 5- or 6-membered aromatic heterocyclic group, and the above sulfur atom is partially or completely substituted by oxygen. It may be completely oxidized. Here, having a sulfur atom is partially oxidized, a sulfoxide group (one SO-), is one that is completely oxidized, a sulfone group - a (-S0 _2). The same applies to the following description.

When having the full sulfonyl group Ya aromatic heterocyclic group substituents, are in this substituent group include a halogen atom, a nitro group, a carboxyl group, Shiano group, C ₁ -C ₄ 7 alkyl group, Ci Among C haloalkyl groups, alkoxyl groups, 〇-〇 haloalkoxyl groups, (C i C anoreoxy) carbonyl groups, Ci C alkylthio groups, CC alkylsulfiel groups and CC alkylsulfonyl groups One or two groups selected from the above can be preferably mentioned.

Of the above R ² , preferred are a hydrogen atom, one or two oxygen atoms and a C to C ₆ alkyl group which may be interrupted by Z or a sulfur atom, and C _{1 to} C ₆ haloalkyl group or a C ₃ -C ₆ cycloalkyl group, more a phenyl group can ani gel, hydrogen atom及Pi 0 ₁ ~ is as more preferable. ₄ Alkyl groups can be mentioned, and particularly preferred are a hydrogen atom and a methyl group.

R ³ may be interrupted by a hydrogen atom, one or two oxygen atoms and a hydrogen atom or a sulfur atom, and may have a halogen atom. Ci Cs chain alkyl group or C ₃ -C ₆ ring Fushimi alkyl or C ₂ -C ₆ alkenyl group,, C ₂ -C ₆ Haroa alkenyl group, or c ₂ to c ₆ shows an alkynyl group, the sulfur atom is optionally be part partial or completely oxidized by oxygen Is also good.

Among such R ³ , preferred are a C ₆ -C ₆ alkyl group, a haloalkyl group and a C ₃ -C ₆ alkyl group which may be interrupted by a hydrogen atom, one or two oxygen atoms and / or a sulfur atom. A C ₆ cycloalkyl group can be mentioned, and more preferred are a hydrogen atom and _{1 to 4} alkyl groups. Particularly preferred are a methyl group, an ethynole group and an isopropyl group. be able to.

R ⁴ may be interrupted by a hydrogen atom, one or two oxygen atoms and Z or sulfur atoms, and may have a halogen atom. Ci-C ₆ chain alkyl group, or C ₂ -C ₆ Aruke - group, C ₂ -C ₆ Haroaruke - group, c ₂ to c ₆ alkynyl group, a Shiano group, forces Rupokishiru group or (Ci Ca alkoxy) carbonylation group, the sulfur atom It may be partially or completely oxidized by oxygen. Among such R ⁴ , preferred are a hydrogen atom, one or two oxygen atoms, and a C ₁ -C ₆ alkyl group which may be interrupted by a Z or sulfur atom. ₁ to. Examples include a _6- haloalkyl group, a carboxyl group and a (C CA alkoxy) carboyl group. More preferred are a hydrogen atom and a C i C alkyl group, and particularly preferred are Represents a hydrogen atom or a methyl group.

R ⁵ is a hydrogen atom, a halogen atom, a nitro group, one or two oxygen atoms and C-C ₆ chain alkyl group or c ₃ -c ₆ cyclic alkyl group which may be interrupted by a sulfur atom and may have a halogen atom, or a carboxyl group, a cyano group, a thiocyano group, ci C alkoxyl group, c to c, Roarukokishiru group, (Ci C alkoxy) carboxamide group, a mercapto group, alkylthio O group, C i~C ₄ alkylsulfinyl group,. ~. Alkylsulfonyl group, C ₂

~C ₆ Arukeyuru group, 〇 ₂ ～〇 ₆ Haroarukeniru group or 〇 ₂ to. ₆ Arukiniru group indicates, the C ~◦ _s chain alkyl or C ₃ -C ₆ sulfur atom in the cyclic alkyl group may be by connexion partially or completely oxidized to oxygen.

Among such R ⁵ , preferred are a halogen atom, an ethoxy group, a CiC ₆ alkyl group optionally interrupted by one or two oxygen atoms and a sulfur or a sulfur atom, or (^ to Flip mouth alkyl group or C ₃ -C ₆ cycloalkyl group, more Shiano group, Ci C alkoxyl group, Ci～C ₄ haloalkoxyl group, c ₁ to c ₄ alkylthio group, C i~C ₄ alkylsulfinyl group and Alkylsulfo

- it can be exemplified group, more preferred are a halogen atom, a nitro group, C ₁ -C ₄ alkyl group, 0 ₁ ～〇 ₄ Haroarukiru groups and 〇 _{1. 4} An alkylsulfonyl group can be mentioned, and a particularly preferable example is a halogen atom, a nitro group and an alkyl group, and a most preferable example is a chlorine atom, a methyl group and an ethyl group. it can.

R ⁶ is a halogen atom, a nitro group, one or two oxygen atoms and // or may be interrupted by a sulfur atom, also a halogen atom which may have a Ci Ce chain alkyl or C ₃ A C ₆ -cyclic alkyl group, or a carboxyl group, a cyano group, a thiocyano group, a C ₁ -C ₄ alkoxyl group. ~ 〇, lower alkoxyl group,

-C ₄ alkoxy) carbonyl group, a mercapto group, an alkylthio group, -C ₄ alkyl sulfide El group, C I～C ₄ alkylsulfonyl group, c ₂ to c ₆ an alkenyl group, C ₂ -C ₆ haloalkenyl group or a C It indicates ₂ -C ₆ alkynyl group, the C i Cs-chain alkyl group or a C ₃ -C ₆ sulfur atoms in the cyclic alkyl group may be by connexion partially or completely oxidized to oxygen.

Among such R ^6, preferred are a halogen atom, - Toromoto, C ₁ -C ₄ alkyl group, 〇 ₁ ～〇 ₄ Haroarukiru Moto及Pi 〇 ₁ ～〇 ₄ Arukirusuruho - be exemplified Le group And more preferred are a halogen atom, a nitro group and . To 〇 alkyl group, and particularly preferred are

An alkyl group can be mentioned, and a most preferred example is a methyl group.

Each of ェ to ⁷ represents an oxygen atom or a sulfur atom, and an oxygen atom is preferred. ¹⁷ and ¹⁸ may each be independently interrupted by a hydrogen atom, a halogen atom, a nitro group, one or two oxygen atoms and / or sulfur atoms, and have a halogen atom. May be C! A C ₆ -chain alkyl group or a C ₃ -C ₆ cyclic alkyl group, or a carboxyl group, a cyano group, a Ci-C ₄ alkoxyl group,

アルキルスルフィニル基， c ₁〜c₄アルキルスルホニル基， 式 一 CHR³⁷N0₂， -CHR³⁷NR¹³R¹⁴, -CHR³⁷P (=0) (OR³⁸)₂， — NR¹³R¹⁴, — NR³⁷COR³⁹' — NR³⁷C0₂R³⁸， 一 NR³⁷S0₂R³⁹， 一 OCOR³⁹， _OCO_¾R³⁷， — OCONR¹³R¹⁴' — OCHR³⁷CN， — O CHR³⁷COR³⁹， -OCHR³⁷C0₂R³⁸, 一 O C HR ³⁷ C O NR ¹³ R ¹⁴， — S0₂NR¹³R¹⁴， 一 OS0₂R³⁹， - O - N = C R ¹³ R ³⁷ , 一 P (=θ) (O R³⁸)₂, -OP (=0) (OR³⁸) ₂で表される基， 置換若しくは無置換のフエ- ル基、 あるいは置換若しくは無置換の 5員又は 6員環の芳香族性複素環式基を示 し、上記 Ci Ce鎖状アルキル基又は C₃〜C₆環状アルキル基に含まれる硫黄原 子は酸素によって部分的若しくは完全に酸化されていてもよい。 Halo anolecoxyl group, (C i -C ₄ anoleoxy) carbonyl group, alkynolethio group, Ci

Alkylsulfinyl group, c ₁ to c ₄ alkylsulfonyl group, wherein one ^{_{CHR 37 N0 2, -CHR 37 NR}} 13 R 14, -CHR 37 P (= 0) (OR 38) 2, - NR 13 R 14, - NR ³⁷ COR ³⁹ '— NR ³⁷ C0 ₂ R ³⁸ , one NR ³⁷ S0 ₂ R ³⁹ , one OCOR ³⁹ , _OCO _¾ R ³⁷ , — OCONR ¹³ R ¹⁴ ' — OCHR ³⁷ CN, — O CHR ³⁷ COR ³⁹ , -OCHR ³⁷ C0 ₂ R ^38, one ^{OC HR 37 CO NR 13 R 14} , - S0 2 NR 13 R 14, one ^{_{OS0 2 R 39, - O -}} N = CR 13 R 37, one ^{P (= θ) (OR 38} ) 2 , -OP (= 0) (OR ³⁸ ) ₂ represents a substituted or unsubstituted phenyl group, or a substituted or unsubstituted 5- or 6-membered aromatic heterocyclic group. The sulfur atom contained in the Ci Ce chain alkyl group or the C ₃ -C ₆ cyclic alkyl group may be partially or completely oxidized by oxygen.

If having the Hue sulfonyl group Ya aromatic heterocyclic group substituents, are in this substituent group include a halogen atom, a nitro group, a carboxyl group, Shiano group, C ₁ -C ₄ 7 alkyl group, Ci ~ C, mouth alkyl group, C alkoxyl group, Ci ~ C, mouth alkoxyl group, ((: -dialkoxy) carbonyl group, alkylthio group, C ₁ -C ₄ alkylsulfinyl group and alkylsulfol group Preferred are one or two groups selected.

Among such R ⁷ and R ⁸ , preferred are a C ₆ -alkyl group which may be interrupted by a hydrogen atom, one or two oxygen atoms and / or sulfur atoms. Ci Ce haloalkyl group, more CC alkoxyl group, Ci C Nono Roarukokishiru group, C i~C ₄ alkylthio group,. ～〇 alkylsulfide el groups, C alkylsulfonyl Moto及Pi formula one _{^{OCOR 39, - OC0 2 R 37}} , one O CONR ¹³ R ^14, one 〇_CHR ^{37 CN, - OC HR 37 COR} 39, - OCHR 37 C 0 2 R 38, can be a group represented by one OCHR ³⁷ CONR ¹³ R ^14, more preferred are A C Ce alkyl group, which may be interrupted by a hydrogen atom, one or two oxygen atoms and a sulfur atom, or a Ci C alkoxyl group; ~. , Can be exemplified mouth alkoxyl group, particularly preferred is assumed, a hydrogen atom, an alkyl Moto及Pi 〇 ₁ ～〇 ₄ alkoxyl group a can and Ageruko, most preferred are a hydrogen atom, a methyl group And methoxy groups.

口アルキル基， — COR³⁹ 又は一 SO ₂R ³⁹を示す。 R ⁹ is a hydrogen atom, a C Cs alkyl group,

Or an alkyl group, — COR ³⁹ or SO ₂ R ³⁹ .

Among these R ⁹ , preferred are a hydrogen atom and ₁ to ₆ alkyl groups, and more preferred are a hydrogen atom, a methyl group and an ethyl group.

R ^1G may be interrupted by a hydrogen atom, one or two oxygen atoms and / or sulfur atoms, and may have a halogen atom. C _{1 to} C ₆ chain alkyl group or c ₃ To c ₆ cyclic alkyl group, or c _{2 to} c ₆ alkyl group, c _{2 to} c ₆ haloalkyl group, C _{2 to} C ₆ alkyl group, or formula — COR ³⁹ , -C 0 ₂ R ³⁷ ,- ^{CH R 37 CN, - CHR 37} COR 39 '- CHR 37 CO 2 R 38, -CHR ^ CONR 1 3 R 14, -CONR 13 R 14, a group represented by -S0 ₂ R ^39, the C Ce The sulfur atom contained in the chain alkyl group or the C ₃ -C ₆ cyclic alkyl group may be partially or completely oxidized by oxygen.

R ¹ like this. Among them, preferred are a hydrogen atom, one or two oxygen atoms and a C to C ₆ alkyl group or a C Cs haloalkyl group which may be interrupted by a Z or sulfur atom, and also a C _{2 to} C _S Arukeeru group, C ₂ -C ₆ Haroaru Kenyir group and C ₂ -C can be mentioned _alkynyl groups, as a more preferable, a hydrogen atom, 〇 ₁ ～〇 ₄ Arukiru Moto及Pi 〇 ₁ 〇 ₄ A halalkyl group can be mentioned, and a particularly preferred example is a methyl group and an ethyl group.

R ¹¹ and R ¹² are each independently a hydrogen atom, a nitro group, a carboxyl group, shea Anomoto, Ci～C ₄ alkyl group, Ji, ~ Ji haloalkyl group, (Ci~C ₄ alkoxy) A carbyl group or 1 COR ³⁹ is shown.

Of these R ¹¹ and R ¹² , preferred are a hydrogen atom,

4 Alkyl groups, C to C, alkyl groups and (CiC alkoxy) carbonyl groups can be mentioned, and more preferred are a hydrogen atom and a CiC alkyl group.

R ¹³ represents a hydrogen atom, Ci Cs alkyl, Ci C port alkyl group or a substituted young properly unsubstituted phenylene Le group.

When the phenyl group has a substituent, examples of the substituent include a halogen atom, a nitro group, a carboxyl group, a cyano group, a C ₁ -C ₄ alkyl group, a C ₁ -C haloalkyl group, and a C i -C ₄ alkoxyl group. , Haloalkoxyl group,

To c ₄ alkoxy) Karuponiru group, C i~C ₄ alkylthio group, C ₁ -C ₄ alkyl Surufieru groups and C i~C ₄ 1 or the like preferably two groups selected from among alkyl sulfo Interview le radical Can be.

Among such R ¹³ , preferred are a hydrogen atom, a Ci Cs alkyl group, or a halogen atom, 〇 _1- . ₄ alkyl groups and ₁ to. _{4 A} phenyl group which may be substituted with one or two groups selected from among alkoxyl groups can be mentioned, and more preferred are a hydrogen atom and ₁ to ₁ . ₄ Alkyl groups can be mentioned.

R ¹⁴ represents a hydrogen atom, a halogen atom, an alkyl group or 〇 to 、, and an alkyl group. Preferred examples of R ¹⁴ include a hydrogen atom and a CC alkyl group, and more preferred examples include a hydrogen atom and a methyl group.

R ^{15 to} R ²³ , R ²⁶ and R ²⁷ are each a hydrogen atom, a halogen atom,. ~ Alkyl group or ~. And a mouth alkyl group. Among them, preferred are a hydrogen atom, a halogen atom and a CiCa alkyl group, and more preferred are a hydrogen atom, a chlorine atom and a methyl group.

R ²⁴及Pi R ²⁵ are each a hydrogen atom, a halogen atom, Ci C alkyl groups, C ～〇 ₄ Haroanorekinore group, Ci C Arukokishinore groups, C ₁ -C ₄ Haroanorekokishi group, a carboxyl group, (Ji ~. Alkoxy ) Carbyl group, Archi A luthio group, CiC alkylsulfiel group, Ci- ₄ alkylsulfonyl group, amino group, mono (CiCalkyl) amino group or di (CiCalkyl) amino group.

Among such R ²⁴ and R ²⁵ , preferred are a hydrogen atom, a halogen atom, a CCA alkyl group, a CiCa haloalkyl group and a to alkoxyl group, and more preferred are , A hydrogen atom, a chlorine atom, a methyl group and a methoxy group.

R ²⁸ , R ²⁹ and R ^{31 to} R ³⁴ each represent a hydrogen atom, a halogen atom, a Ci C alkyl group or a C 1 to C 2 alkyl group. Among them, preferred are a hydrogen atom and ₁ to ₄ alkyl groups, and more preferred are a hydrogen atom and a methyl group.

R ³⁵ and R ³⁶ each independently represent a hydrogen atom, a halogen atom, a CiCT alkyl group, an alkyl group, a force representing an alkoxy group, or R ³⁵ , R ^36, and a bond thereof. When the carbon atoms are joined together, the formula

R ¹⁰

 R 13

May be formed.

Preferred examples of R ³⁵ and R ³⁶ include a hydrogen atom, an alkyl group, a C i -C ₄ alkoxyl group and R ³⁵ , R ³⁶ and the carbon atom to which they are bonded, formula

And those forming a group represented by the following formula. More preferably, a hydrogen atom or a A tyl group, an ethyl group or R ³⁵ , R ³⁶ and the carbon atom to which they are bonded together,

And those forming a group represented by

R ³⁰ , R ³⁷ , R ³⁸ and R ^{4 ()} each represent a hydrogen atom or a CiCa alkyl group. Among them, preferred are a hydrogen atom, a methyl group and an ethyl group.

R ³⁹ represents a CiC alkyl group, di-, di-alkyl group, or substituted or unsubstituted fluorine group. Here, if the phenyl group has a substituent, examples of the substituent include a halogen atom, a nitro group, a force Rupokishiru group, Shiano group, 〇 ~ c ₄ Anorekiru group, C i~C ₄ Haroarukinore group, 〇 ~. Alkoxy group, Ci-C ₄ haloalkoxyl group, (di-dialkoxy) carbonyl group, di-dialkylthio group, CCA alkylsulfur group and the like. Preferable examples are one or two groups selected from alkyl sulfol groups.

Among such R ³⁹ , preferred is a Ci C alkyl group. Yeah ~

アルコキシル基の中から選ばれる 1又は 2個の基で置換されていてもよいフエ- ル基を挙げることができ、 より好ましいものとしては、 Ci C アルキル基を挙 げることができる。 A C ₄ haloalkyl group or a halogen atom. ~. Alkyl group and

Examples include a phenyl group which may be substituted with one or two groups selected from alkoxyl groups, and more preferred examples include a CiC alkyl group.

Among the various groups, in one or two C _t -C ₆ chain alkyl or C ₃ -C ₆ cyclic alkyl group optionally interrupted by an oxygen atom and Roh or a sulfur atom, C ~ Examples of C ₆ alkyl groups (chained) include the formulas CH ₂ X ⁸ CH ₃ , CH ₂ X ⁸ CH ₂ CH ₃ , CH ₂ X ⁸ CH ₂ CH ₂ CH ₃ , — CH ₂ CH ₂ X ⁸ CH ₃ , -CH ₂ CH ₂ X ⁸ CH ₂ CH ₃ , — CH (CH ₃ ) X ⁸ CH ₂ CH ₃ , -CH ₂ X ⁸ CH (CH ₃ ) ₂ , CH ₂ X ⁸ C (CH ₃ ) ₃ , -CH ₂ X ⁸ CH (CH ₂ CH ₃ ) ₂ , -CH ₂ X ⁸ CH ₂ CH ₂ X ⁹ CH ₃ , One CH ₂ X ⁸ CH ₂ CH ₂ X ⁹ CH ₂ CH ₃ ,-CH ₂ X A group represented by ⁸ CH ₂ CH ₂ X CH (CH ₃ ) ₂ can be exemplified. In addition, C is interrupted by one or two oxygen atoms and / or sulfur atoms and has a halogen atom. Among -C ₆ linear alkyl or C ₃ -C ₆ cyclic alkyl group, c ₁ to c ₆ The Haroaruki Le group (chain), for example, one of the above-exemplified or two oxygen atoms及Pi Z Or one in which one or more hydrogen atoms of a _6- alkyl group (chain) interrupted by a sulfur atom is replaced by a halogen atom, specifically, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. be able to.

Further, among C i Ce chain alkyl groups or C ₃ -C ₆ cyclic alkyl groups interrupted by one or two oxygen atoms and Z or sulfur atoms, C ₃ -C ₆ cycloalkyl groups For example, the expression

And the like.

X ⁸ and X ⁹ each represent an oxygen atom or a sulfur atom. In the case of a sulfur atom, they are partially oxidized to sulfoxide (so) or completely oxidized to sulfon (so ₂ ). You may.

 n represents 0 or 1.

and q each represent 0, 1 or 2, and when p is 2, two R ²⁴ may be the same or different, and when q is 2, two R ⁶ may each be They may be the same or different. M is preferably 2, and p and q are each preferably 0 or 1.

Among the acetylene derivatives represented by the general formula (I), preferred are those represented by the general formula (Ia) (I-a)

(Where R ¹ ! ^ ⁶ , X ¹ , X, Y, Z and q are the same as above.)

Can be mentioned.

The compound represented by the above general formula (I-a) has a structure in which a pyrazolyl group is bonded to the R ^{5 of} the benzene ring at the o-position through one C (= ^XX ). . In this general formula (I-a), X is

(In the formula, R ⁷ , R ⁸ and R ¹⁰ are the same as described above.)

The group represented by, Y is the formula

R ²⁸ R ²⁸ R 31

One c— or one c— C-K ²⁹ R ²⁹ R ³²

(In the formula, R ²⁸ , R ²⁹ , R ³¹ and R ³² are the same as described above.)

And Z is a group represented by the formula

 ― S

o _m

(In the formula, m is the same as described above.)

Those which are groups represented by are particularly preferable.

は前言己と 同じである。） Such compounds include compounds represented by the general formula (Ib), the general formula (I-c), the general formula (I-d) or the general formula (I-e)

Is the same as the previous statement. )

Can be mentioned.

 Among the acetylene derivatives represented by the general formula (I), when the compound can form a salt, the salt is also included in the acetylene derivative of the present invention. INDUSTRIAL APPLICABILITY The acetylene derivative of the present invention does not cause phytotoxicity to field cultivated crops such as corn, has excellent herbicidal activity, and can control a wide range of field weeds at a low dose.

Next, a method for producing the acetylene derivative of the present invention represented by the general formula (I) explain.

The acetylene derivative, for example, the compound represented by the general formula () wherein X ¹ in the general formula (I) is an oxygen atom is represented by the following reaction formula:

 (I I)

 [Method A] [Method B]

R ¹ — C≡C— C

 (in)

 (r)

(In the formula,! ^ ¹ to! ^ X, Υ, Ζ, and q are the same as above.)

(Method A) in which a pyrazole derivative of the general formula (II) is reacted with a hachigen compound of the general formula (III), and a pyrazole derivative of the general formula 1) is reacted with the general formula (IV). Can be produced by a method (method B) of reacting with alcohol. Method A

In this method, a pyrazole derivative of the general formula (II) is reacted with a halogenic compound of the general formula (III) in an inert solvent in the presence of a hydrogen halide scavenger to obtain a compound of the general formula (III). 1 ′) is produced. In this reaction, the halogen compound of the general formula (III) is added to one mole of the virazole derivative of the general formula (II). 'It is generally preferred to use 1 to 3 moles. As the hydrogen halide scavenger, for example, bases such as sodium carbonate, potassium carbonate, triethylamine and pyridine are used. These hydrogen halide scavengers are preferably used in an amount equal to or greater than the amount of the compound of the general formula (Π), and the reaction temperature is preferably in the range from room temperature to the boiling point of the solvent used. . Examples of the inert solvent include aromatic hydrocarbons such as benzene and toluene, ethers such as getyl ether, ketones such as methylethyl ketone, and halogenated hydrocarbons such as dichloromethane, chlorohonolem, and dichloroethane.

 B method

 In this method, a pyrazolyl derivative of the general formula (II) is reacted with an alcohol of the general formula (IV) in an inert solvent in the presence of a dehydrating condensing agent such as azodicarboxylic acid diester or triphenylphosphine. As a result, a compound represented by the general formula (1 ′) is produced. In this reaction, the alcohol of the general formula (IV) is preferably used in a proportion of generally 1 to 2 mol per mol of the pyrazole derivative of the general formula (II). The reaction temperature is preferably in the range from room temperature to the boiling point of the solvent used. Examples of the inert solvent include, for example, aromatic hydrocarbons such as benzene and toluene, ethers such as diethyl / leethenole, halogenated hydrocarbons such as dichloromethane, chloroform / lem, and dichloroethane.

The compound represented by the general formula (1 ") wherein X ¹ in the general formula (I) is a sulfur atom is represented by the following reaction formula

 (1 ")

(In the formula, R ¹ ! ^ ⁶ : X, Υ, Z and q are the same as described above.)

As shown in the above, the compound represented by the general formula (1 ′) is reacted with a Lawesson reagent in an inert solvent: Generally, it is preferable to use 1-2 equivalents of the Lawesson reagent with respect to the pyrazole derivative (1 ′). The reaction temperature is preferably in the range from room temperature to the boiling point of the solvent used. Examples of the solvent used for the reaction include aromatic hydrocarbons such as benzene and toluene, and ethers such as getyl ether and dimethoxetane.

 The pyrazole derivative represented by the general formula (II) can be prepared by a known method (for example, WO93 / 18031, WO94 / 01431, WO95 / 4054, W096 / 25412, W095 / 13275,

WO96 / 30368, WO96 / 31507, W097 / 12885, WO97 / 19087, W097 / 42185, WO97 / 01550, WO97 / 03045, WO97 / 08164, W098 / 28291, WO97 / 30986, WO97 / 30993, WO98 / 12180, W098 / 12192, W098 / 49159, W098 / 35954, special (Kaihei 7-291970, JP-A-7-316149, USP5607898, USP5631210, USP5723411, USP5885936, DE4427996, DE4427997, DE19532312, etc.).

 The herbicide of the present invention contains, as an active ingredient, the acetylene derivative of the present invention represented by the general formula (1) and Z or a salt thereof as an active ingredient. These compounds are used as a liquid carrier such as a solvent or a mineral substance. It can be mixed with a solid carrier such as fine powder and formulated into wettable powders, emulsions, powders, granules, etc. for use. Surfactants may be added to provide emulsification, dispersibility, spreadability, etc. during formulation. When the herbicide of the present invention is used in the form of a wettable powder, the acetylene derivative of the present invention and / or a salt thereof is usually added at a rate of 10 to 55% by weight. The composition may be prepared by blending the solid carrier in an amount of 40 to 88% by weight and the surfactant in an amount of 2 to 5% by weight. When used in the form of a paste, the acetylene derivative of the present invention and / or a salt thereof is usually 20 to 50% by weight, and the solid carrier is 35 to 75% by weight. /. And surfactant 5 to: The composition may be prepared by mixing at a ratio of 15% by weight. On the other hand, when used in the form of a powder, the acetylene derivative of the present invention and / or its salt are usually 1 to 15% by weight, 80 to 97% by weight of a solid carrier and 2 to 5% by weight of a surfactant. To prepare a composition. When used in the form of granules, the acetylene derivative of the present invention and / or a salt thereof is usually blended in a proportion of 1 to 15% by weight, a solid carrier in an amount of 80 to 97% by weight, and a surfactant in a proportion of 2 to 5% by weight. The composition may be prepared by heating.

 Here, fine powder of a mineral substance is used as the solid carrier. Examples of the fine powder of the mineral substance include oxides such as diatomaceous earth and slaked lime, phosphates such as apatite, sulfates such as Secco, talc, and the like. Pai-mouth ferrite, clay, kaolin, bentonite, acid clay, white carbon, quartz powder, and silicates such as kaite powder.

Organic solvents are used as the solvent. Specific examples include aromatic hydrocarbons such as benzene, toluene, and xylene; chlorinated hydrocarbons such as 0-chlorotoluene, trichloroethane and trichloroethylene; cyclohexanol; Amanol alcohol, ethylene glycol / vinyl alcohol, etc., isophorone, cyclohexanone, cyclohexenyl-cyclohexanone, ketones, etc. And esters such as methyl phthalate, amides such as dimethylformamide, and mixtures thereof. Can be .

 Examples of the surfactant include aion type (fatty acid salt, alkyl sulfate, a / lex / lebenzenesulfonic acid, dianolex / resulfosuccinate, alkynolephosphate, salt of naphthalenesulfonic acid-formalin condensate, polyoxygen salt). Ethylenealkyl sulfate, etc., Noon type (polyoxyethylene alkyl ether, polyoxyethylene alkyl phenylene ether, polyoxyethylene alkyl ester, polyoxyethylene alkylamine, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, etc. ), Cationic type or amphoteric type (amino acid, betaine, etc.) can be used.

 The herbicide of the present invention may contain other herbicidal active ingredients, if necessary, together with the acetylene derivative represented by the general formula (I) and / or its salt as an active ingredient. Examples of such other herbicidally active ingredients include conventionally known herbicides such as phenoxy, diphenyl ether, triazine, urea, carbamate, thiocarbamate, acid alide, acetylene, and phosphorus. An acid type, a sulfonylurea type, an oxadiazone type and the like can be mentioned, and these can be appropriately selected and used from these herbicides.

 Furthermore, the herbicide of the present invention can be mixed with an insecticide, a bactericide, a plant growth regulator, a fertilizer, and the like, if necessary.

The herbicide of the present invention can be used as a herbicide for upland fields in any of soil treatment, soil admixture treatment and foliage treatment. As the field weeds (Cropland weeds) targeted by the compound of the present invention, for example, Solanaceae weeds represented by Solanum nigrum, Datura stramonium, etc., Almtilon theophrasti, and American stag beetle Malvaceae weeds such as (Sida spinosa), convolvulaceae weeds such as Ipomoea spps. Such as Malva morning glory (Ipomoea purpurea), and convolvulus (Calystegia spps.) , Amaranthaceae (Amaranthaceae) typified by Amaranthus lividus, etc., Xanthium strumarium, Ragweed (Ambrosia artemisiaefolia), Helianthus (Helianthus annus), lian Asteraceae represented by cicada (Cirsium arvense), nopolgum (Senecio vulgaris), and shrimp (Erigeron annus) (Compositae) Weed, cruciferae (Cruciferae) represented by weeds (Rorippa indica), wild ash (Sinapis arvensis), napsuna (Capsellaureabursa—pastoris), etc. Polygonaceae (Polygonaceae) weeds, Portulaca oleracea (Portulaca oleracea), etc.

 (Chenopodi m album), Chenopodium ficifolium, Kouki (Kchia scop aria), etc., and Akaza (Chenopodiaceae) weeds. Scrophulariaceae, represented by (Veronica persica), etc., and communis (CommeHna communis), etc.

 (Commelinaceae) Weeds, Labiatae weeds represented by Lamium amplexicaule (Lamium purpureum), etc. Weeds, Echinacea (Euphorbia maculata), etc. ) Weeds, Rubiaceae weeds such as Galium spurium, Galium aparine, Rubia akane Weeds, and violets such as violets (Viola arvensis) ) Weeds, Broad-leaved weeds such as legumes (Leguminosae) weeds such as Sesbania exaltata and Cassia obtusifolia, wild sorghum (Sorgham bicolor), (panicum dichotomiflorum Johnsongrass (Sorghum

 alepense), barnyardgrass (Ec inochloa cr s-galli), mexisino (Digitaria adscendens), oats (Avena fat a), ohisino (Eleusine indica), enocologosa (Setaria viridis), sparrows (Alopeis ae) Examples include Cyperaceous weeds, such as Graminaceous weeds, and Cyperus rot ndus, Cyper s esculentus, and the like.

Further, the compound of the present invention can be used as a herbicide for paddy fields in any of soil treatment and foliage treatment under flooding. Examples of paddy weeds include paddy weeds, such as Alisma canaliculatum, Sagittaria trifolia, and Sagittaria pygmaea. The weeds of the stag beetles (Cyperaceae) (Cyperaceae) inhabited by the crabs of the sect. Scrothuslariaceae) Weeds, Potenderiaceae weeds such as monochoria (Monochoria Vaginalis), $ 1 grasses such as Potamogetonaceae such as Polgeton distinctus, etc. Examples include Lythraceae weeds and Gramineae weeds such as Ecliinochloa crus-galli.

The effective application amount of the compound of the present invention for weeding can be determined in consideration of various conditions such as the form of the preparation, the application method, the type and amount of the weeds, and the growth condition. It is usually 0.001 to 3.0 kg / ha, preferably 0.01 to 0.31 ^ _§ / 11 &, and those skilled in the art can easily determine the effective amount for obtaining the required herbicidal effect.

 Next, the present invention will be described in more detail with reference to production examples and herbicide examples. The present invention is not limited to these examples.

Production Example 1

 5- (1'-Methyl-1 5'-Propargyloxypyrazole 4,1 yl) Potassinolone 3,3,4-Trimethinolee 2,3-dihydrobenzothiophene 1,11-Dioxide (Compound IX-1 )

 (1) Method A

 5-(-Methynolee 5 '—Hydroxypyrazole-4'-Isle) Canoleponinolee 3,3,4-Trimethyi / lee 2,3-Dihydrobenzothiophene 1,1-dioxodide 0.50 g (1.5 mmol) in 5 ml of acetone After dissolution, 0.31 g (2.2 mmol) of potassium carbonate, 0.21 g (1.8 mmol) of propargyl bromide, and tetrabutylammonium iodide (catalytic amount) were added. Then, the mixture was stirred at room temperature for one day. After completion of the reaction, the solvent was distilled off under reduced pressure. The obtained oil was purified by silica gel column chromatography, and 5- (1'-methyl-5'-propargyloxypyrazole-4'-yl) carbo-leu 3,3,4-trimethinol-1,2,3-diethyl 0.07 g (13% yield) of drobenzothiophene 1,1-dioxide was obtained.

(2) Method B 5— (1'-methinole-5'-hydroxypyrazonole-1 ') Canolepoenole 3,3,4-trimethinole 2,3-dihydrobenzothiophene 1,1 dioxode 3.0 g (9.0 mmol) Was dissolved in 30 ml of benzene, and trifenylphosphine 2.4 g (9.2 mmol), 3.9 g (9.0 mmol) of azodicarboxylic acid geronate (40% by weight in toluene) and 0.51 g (9.1 mmol) of propargyl alcohol were added. For 1 day. After completion of the reaction, the solvent was distilled off under reduced pressure. The obtained oil was purified by silica gel column chromatography, and the obtained solid was recrystallized from ethanol to give 5- (1'-methyl-5'-propargyloxypyrazole-4'-yl) carbonitrile. 1.4 g (yield 41%) of 3,3,4-trimethyl-2,3-dihydrobenzothiophene 1,1-dioxide was obtained.

 The following compounds I to ΧΠΙ can be synthesized by the above methods A and B. (1) Compound I1-1: 1—1188

Compounds 1-1 to 1-1188 are compounds represented by the general formula (1b), and the substituents 1 ^ to ¹⁶ of each compound have the structure shown in the row of the corresponding number in Table 1. Have.

 (2) Compound II-1 -II-1188

Compound II—1 ~! I-1188 is a compound represented by the general formula (Γ-c), and the substituents R ^{1 to} R ⁶ of each compound have a structure shown in the row of the corresponding number in Table 1.

 (3) Compound III 1-III-1188

Compound III-1 to: [II-1188 is a compound represented by the general formula (_d), and the substituents R ^{1 to} R ⁶ of each compound are shown in the row of the corresponding number in Table 1. It has a structure.

(1, -d)

 (4) Compounds IV-1 to IV-1188

Compounds IV-1 to IV-1188 are compounds represented by the general formula (_e), and the substituents R ^{1 to} R ⁶ of each compound have a structure shown in the row of the corresponding number in Table 1. .

(1, -e)

(5) Compound V—1 to V—1 188

Compounds V-1 to V-1188 are compounds represented by the general formula (1f), and the substituents 1 ^ to ¹⁶ of each compound have a structure shown in the row of the corresponding number in Table 1. . (I 'one f)

 (6) Compound VI-1 to VI-1188

Compound VI- 1~VI- 1188 is the substituent RR ⁶ compound of general formula a and each of the compounds represented by (one g) having the shown in the corresponding row of numbers structure in the first table.

 (7) Compound VII — 1 to VII-1188

Compounds VII-1 to VII-1188 are compounds represented by the general formula (1h), and the substituents R to ⁶ of each compound have a structure shown in the row of the corresponding number in Table 1. .

(Ι 'one h)

 (8) Compounds VIII-1 to VIII-1188

Compounds VIII-1 to VIII-1188 are compounds represented by the general formula (I′-i), and the substituents R i to R ⁶ of each compound are shown in the row of the corresponding number in Table 1. Having a structure.

(9) Compound IX-1 to: [X-1188

Compounds IX—1 to IX—1188 are compounds represented by the general formula (I′—j), and the substituent R ェ to scale ⁶ of each compound is shown in the row of the corresponding number in Table 1. Having a structure.

(1, -j)

Compounds X—1 to X—1188 are compounds represented by the general formula (I′—k), and the substituents R ^{1 to} R ⁶ of each compound have the structure shown in the row of the corresponding number in Table 1. Having.

(1, -k)

(11) Compound XI-1 to: I-1188

Compound XI-1 to: XI-1188 is a compound represented by the general formula (I ′ 11), and the substituent ⁶ of each compound has a structure shown in the row of the corresponding number in Table 1. . (Ι 'ichi 1)

 (12) Compound XII — 1 to ΧΠ-1188

Compounds XII-1 to ΧΙΙ-1188 are compounds represented by the general formula (I′-1 m), and the substituents R i to R ⁶ of each compound are shown in the row of the corresponding number in Table 1. Having a structure.

 (13) Compounds XIII-1 to XIII-1188

Compound XIII- 1~ΧΙΠ- 1188 is Ri compound der represented by the general formula (I 'one eta), the substituents R to R ⁶ of each compound were shown in the row of numbers corresponding in the second table structure Having.

 In Tables 1 and 2, Et: ethyl group, n-Pr: n-propyl group, i-Pr: isopropyl group, n-Bu: n-butyl group, i-1 Bu: isobutyl group, t-1 Bu: tert-butyl group, Ph: fuel group, TMS: trimethylsilyl group.

Table 3 shows the NMR and IR spectrum data of typical compounds of the present invention. Table 1-

Rl R2 R3 ^J R4 R5 R6

H H CH3 H CH3 H

CH3 H CH3 H CH3 H

Et H CH3 H CH3 H n-Pr H CH3 H CH3 H i-Pr H CH3 H CH3 H n-Bu H CH3 H CH3 H i-Bu H CH3 H CH3 H t-Bu H CH3 H CH3 H

CH2C1 H CH3 H CH3 H

Ph H CH3 H CH3 H

TMS H CH3 H CH3 H

H CH3 CH3 H CH3 H

CH3 CH3 CH3 H CH3 H

Et CH3 CH3 H CH3 H n-Pr CH3 CH3 H CH3 H i-Pr CH3 CH3 H CH3 H n-Bu CH3 CH3 H CH3 H i-Bu CH3 CH3 H CH3 H t-Bu CH3 CHS H CH3 H

CH2C1 CH3 CH3 H CH3 H

Ph CH3 CH3 H CH3 H

TMS CH3 CH3 H CH3 H

H Et CH3 H CH3 H

CH3 Et CH3 H CH3 H

Et Et CH3 H CH3 H n-Pr Et CH3 H CH3 H i-Pr Et CH3 H CH3 H n-Bu Et CH3 H CH3 Hi i-Bu Et CH3 H CH3 H t-Bu Et CH3 H CH3 H

CH2C1 Et CH3 H CH3 H

Ph Et CH3 H CH3 H

TMS Et CH3 H CH3 H

H H CH3 CH3 CH3 H

CH3 H CH3 CH3 CH3 H

Et H CH3 CH3 CH3 H n-Pr H CH3 CH3 CH3 H i-Pr H CH3 CH3 CH3 H n-Bu H CH3 CH3 CH3 Hi i-Bu H CH3 CH3 CH3 H t-Bu H CH3 CH3 CH3 H

CH2C1 H CH3. CH3 CH3 H

Ph H CH3 CH3 CH3 H

TMS H CH3 CH3 CH3 H

H CH3 CH3 CH3 CH3 H

CH3 CH3 CH3 CH3 CH3 H

Et CH3 CH3 CH3 CH3 H n-Pr CH3 CH3 CH3 CH3 Hi-Pr CH3 CH3 CH3 CH3 H n-Bu CH3 GH3 CH3 CH3 H Table 1 I 2

 Rl R2 R3 R4 R5 R6 i-Bu CH3 CH3 CH3 CH3 H t-Bu CH3 CH3 CH3 CH3 H

CH2C1 CH3 CH3 CH3 CH3 H

Ph CH3 CH3 CH3 CH3 H

TMS CH3 CH3 CH3 CH3 H

H Et CH3 CH3 CH3 H

CH3 Et CH3 CH3 CH3 H

Et Et CH3 CH3 CH3 H n-Pr Et CH3 CH3 CH3 Hi i-Pr Et CH3 CH3 CH3 H n-B Et CH3 CH3 CH3 Hi i-Bu Et CH3 CH3 CH3 H t-Bu Et CH3 CH3 CH3 H

CH2C1 Et CH3 CH3 CH3 H

Ph Et CH3 CH3 CH3 H

TMS Et CH3 CH3 CH3 H

H H Et H CH3 H

CH3 H Et H CH3 H

Et H Et H CH3 H n-Pr H Et H CH3 H i-Pr H Et H CH3 H n-Bu H Et H CH3 H i-Bu H Et H CH3 H t-Bu H Et H CH3 H

CH2C1 H Et H CH3 H

Ph H Et H CH3 H

TMS H Et H CH3 H

H CH3 Et H CH3 H

CH3 CH3 Et H CH3 H

Et CH3 Et H CH3 H n-Pr CH3 Et H CH3 Hi i-Pr CH3 Et H CH3 H n-Bu CH3 Et H CH3 Hi i-Bu CH3 Et H CH3 H t-Bu CH3 Et H CH3 H

CH2C1 CH3 Et H CH3 H

Ph CH3 Et H CH3 H

TMS CH3 Et H CH3 H

H Et Et H CH3 H

CH3 Et Et H CH3 H

Et Et Et H CH3 H n-Pr Et Et H CH3 Hi-Pr Et Et H CH3 H n-Bu Et Et H CH3 Hi-Bu Et Et H CH3 H t-Bu Et Et H CH3 H

CH2C1 Et Et H CH3 H

Ph Et Et H CH3 H

TMS Et Et H CH3 H

HH Et CH3 CH3 H H 8H0 H 8HO OSI

H H ¾R SHO 6fl

H mo H 6HO 8

H 8H0 H SHO m

H 8H0 H SHO

 H 6H0 H SHO 6HO

 H 8H0 H 8HO H m

H SHO H W H Sou sn

H 2R0 H H zn

H 8H0 H H 10SHO in

H SHO H H ng on

H 8H0 H H 68T

H 8H0 H ¾-ϊ H 88T

H 8H0 H H ¾-T L l

H SHO H H 981

H 8H0 H W H 98ΐ

H 8H0 H H 8HO Ψ2Τ

H 8H0 H H H 88T

H SHO 8HO SHI S8T

H 8HO 8HO ^ d T8T

H SHO 8HO 10SHO οετ

H 8HO 8HO ng 6δΤ

H 8HO SHO a 8ST

H SHO 8HO LZl

H SHO 8HO ¾-ϊ 9δΤ

 H 8HO 8HO 8HO SKA \ ζ \

H 8HO 8HO SHO ^ d 0ST

H 8HO SHO 8HO 10SHO 6ΤΤ

H 8HD 8HO SHO ng4 8Τΐ

. H SHO 8HO SHO ι \\

H 8HO SHO 8HO 9ΤΙ

H SHO SHO SHO 9ττ

H SHO 8HO SHO ητ

H 8HO 8HO SHO ειτ

 H 8HO SHO 8HO H XIX

H SHO SHO H SHX ΟΤΐ

H 8HO 8HO H 60Τ

H 8HO 8HO H IOSHO Xie

H SHO 8HO H LOT

H 8HO 8HO H 90ΐ

H 8HO 8HO H ng-u SOI

H QUO SHO H ¾-ϊ

 H 8HO SHO H 80Τ

H SHO 8HO H SOI

H 8HO 8HO H SHO TOT

9Ή 8H z

 ε— 挲 I 绻

oiieo / iodf / x3 <i 6616Ζ. / Ϊ0 OAV Table 1—4

 No. Rl R2 R3 R4 R5 R6

151 t-Bu CH3 i-Pr H CH3 H

152 CH2C1 CH3 i-Pr H CH3 H

153 Ph CH3 i-Pr H CH3 H

154 TMS CH3 i-Pr H CH3 H

155 H Et i-Pr H CH3 H

156 CH3 Et i-Pr H CH3 H

157 Et Et i-Pr H CH3 H

158 n-Pr Et i-Pr H CH3 H

159 i-Pr Et i-Pr H CH3 H

160 n-B Et i-Pr H CH3 H

161 i-Bu Et i-Pr H CH3 H

162 t-Bu Et i-Pr H CH3-H

163 CH2C1 Eti-Pr H CH3 H

164 Ph Et i-Pr H CH3 H

165 TMS Et i-Pr H CH3 H

166 H H i-Pr CH3 CH3 H

167 CH3 H i-Pr CH3 CH3 H

168 Et H i-Pr CH3 CH3 H

169 n-Pr H i-Pr CH3 CH3 H

170 i-Pr H i-Pr CH3 CH3 H

171 n-Bu H i-Pr CH3 CH3 H

172 i-Bu H i-Pr CH3 CH3 H

173 t-Bu H i-Pr CH3 CH3 H

174 CH2C1 H i-Pr CH3 CH3 H

175 Ph H i-Pr CH3 CH3 H

176 TMS Hi i-Pr CH3 CH3 H

177 H CH3 i-Pr CH3 CH3 H

178 CH3 CH3 i-Pr CH3 CH3 H

179 Et CH3 i-Pr CH3 CH3 H

180 n-Pr CH3 i-Pr CH3 CH3 H

181 i-Pr CH3 i-Pr CH3 CH3 H

182 n-Bu. CH3 i-Pr CH3 CH3 H

183 i-Bu CH3 i-Pr CH3 CH3 H

184 t-Bu CH3 i-Pr CH3 CH3 H

185 CH2C1 CH3 i-Pr CH3 CH3 H

186 Ph CH3 i-Pr CH3 CH3 H

187 TMS CH3 i-Pr CH3 CH3 H

188 H Et i-Pr CH3 CH3 H

189 CH3 Et i-Pr CH3 CH3 H

190 Et Et i-Pr CH3 CH3 H

191 n-Pr Et i-Pr CH3 CH3 H

192 i-Pr Et i-Pr CH3 CH3 H

193 n-Bu Et i-Pr CH3 CH3 H

194 i-Bu Et i-Pr CH3 CH3 H

195 t-Bu Et i-Pr CH3 CH3 H

196 CH2C1 Et i-Pr CH3 CH3 H

197 Ph Et i-Pr CH3 CH3 H

198 TMS Et i-Pr CH3 CH3 H

199 H H CH3 H CH3 CH3

200 CH3 H CH3 H CH3 CH3 Table 1-5

 No. Rl R2 R3 R4 R5 R6

201 Et H CH3 H CH3 CH3

202 n-Pr H CH3 H CH3 CH3

203 i-Pr H CH3 H CH3 CH3

204 n-Bu H CH3 H CH3 CH3

205 i-Bu H CH3 H CH3 CH3

206 t-Bu H CH3 H CH3 CH3

207 CH2C1 H CH3 H CH3 CH3

208 Ph H CH3 H CH3 CH3

209 TMS H CH3 H CH3 CH3

210 H CH3 CH3 H CH3 CH3

211 CH3 CH3 CH3 H CH3 CH3

212 Et CH3 CH3 H CH3 CH3

213 n-Pr CH3 CH3 H CH3 CH3

214 i-Pr CH3 CH3 H CH3 CH3

215 n-Bu CH3 CH3 H CH3 CH3

216 i-Bu CH3 CH3 H CH3 CH3

217 t-Bu CH3 CH3 H CH3 CH3

218 CH2C1 CH3 CH3 H CH3 CH3

219 Ph CH3 CH3 H CH3 CH3

220 TMS CH3 CH3 H CH3 CH3

221 H Et CH3 H CH3 CH3

222 CH3 Et CH3 H CH3 CH3

223 Et Et CH3 H CH3 CH3

224 n-Pr Et CH3 H CH3 CH3

225 i-Pr Et CH3 H CH3 CH3

226 n-Bu Et CH3 H CH3 CH3

227 i-Bu Et CH3 H CH3 CH3

228 t-Bu Et CH3 H CH3 CH3

229 CH2C1 Et CH3 H CH3 CH3

230 Ph Et CH3 H CH3 CH3

231 TMS Et CH3 H CH3 CH3

232 H H CH3 CH3 CH3 CH3

233 CH3 H CH3 CH3 CH3 CH3

234 Et H CH3 CH3 CH3 CH3

235 n-Pr H CH3 CH3 CH3 CH3

236 i-Pr H CH3 CH3 CH3 CH3

237 n-Bu H CH3 CH3 CH3 CH3

238 i-Bu H CH3 CH3 CH3 CH3

239 t-Bu H CH3 CH3 CH3 CH3

240 CH2C1 H CH3 CH3 CH3 CH3

241 Ph H CH3 CH3 CH3 CH3

242 TMS H CH3 CH3 CH3 CH3

243 H CH3 CH3 CH3 CH3 CH3

244 CH3 CH3 CH3 CH3 CH3 CH3

245 Et CH3 CH3 CH3 CH3 CH3

246 n-Pr CH3 CH3 CH3 CH3 CH3

247 i-Pr CH3 GH3 CH3 CH3 CH3

248 n-Bu CH3 CH3 CH3 CH3 CH3

249 i-Bu CH3 CH3 CH3 CH3 CH3

250 t-Bu CH3 CH3 CH3 CH3 CH3 Table 1-6

 No. Rl R2 R3 R4 R5 R6

251 CH2C1 CH3 CH3 CH3 CH3 CH3

252 Ph CH3 CH3 CH3 CH3 CH3

253 TMS CH3 CH3 CH3 CH3 CH3

254 H Et CH3 CH3 CH3 CH3

255 CH3 Et CH3 CH3 CH3 CH3

256 Et Et CH3 CH3 CH3 CH3

257 n-Pr Et CH3 CH3 CH3 CH3

258 i-Pr Et CH3 CH3 CH3 CH3

259 n-Bu Et CH3 CH3 CH3 CH3

260 i-B Et CH3 CH3 CH3 CH3

261 t-Bu Et CH3 CH3 CH3 CH3

262 CH2C1 Et CH3 CH3 CH3 CH3

263 Ph Et CH3 CH3 CH3 CH3

264 TMS Et CH3 CH3 CH3 CH3

265 H H Et H CH3 CH3

266 CH3 H Et H CH3 CH3

267 'Et H Et H CH3 CH3

268 n-Pr H Et H CH3 CH3

269 'i-Pr H Et H CH3 CH3

270 n-Bu H Et H CH3 CH3

271 i-Bu H Et H CH3 CH3

272 t-Bu H Et H CH3 CH3

273 CH2C1 H Et H CH3 CH3

274 Ph H Et H CH3 CH3

275TMS H Et H CH3 CH3

276 H CH3 Et H CH3 CH3

277 CH3 CH3 • Et H CH3 CH3

278 Et CH3 Et H CH3 CH3

279 n-Pr CH3 Et H CH3 CH3

280 i-Pr CH3 Et H CH3 CH3

281 n-Bu CH3 Et H CH3 CH3

282 i-Bu CH3 Et H CH3 CH3

283 t-Bu CH3 Et H CH3 CH3

284 CH2C1 CH3 Et H CH3 CH3

285 Ph CH3 Et H CH3 CH3

286 TMS CH3 Et H CH3 CH3

287 H Et Et H CH3 CH3

288 CH3 Et Et H CH3 CH3

289 Et Et Et H CH3 CH3

290 n-Pr Et Et H CH3 CH3

291 i-Pr Et Et H CH3 CH3

292 n-Bu Et Et H CH3 CH3

293 i-Bu Et Et H CH3 CH3

294 t-Bu Et Et H CH3 CH3

295 CH2C1 Et Et H CH3 CH3

296 Ph Et Et H CH3 CH3

297 TMS Et Et H CH3 CH3

298 H H Et CH3 CH3 CH3

299 CH3 H Et CH3 CH3 CH3

300 Et H Et CH3 CH3 CH3 8H0 8HO H 8HO 10SHO OQB

8H0 8HO H 8HO ng- 6f8

8H0 8HO H SHO ng-i 8 ^ 8

8H0 8HO H 8HO Lf

8H0 8HO H SHO d-ΐ 9 ^ 8

8H0 8HD H 8HO 9f £

8H0 8HO H 8HO ffB

9H0 8HO H d-ΐ 8HO 8HO 8 ^ 8

8H0 8HO H ¾- | SHO H ΖΨ2

8H0 8HO H -ΐ H SHJL ΙΨ2

8H0 8HO H ¾-ϊ H OfS

8H0 8HO H ¾- | H TOSHO 688

8H0 8HO H H ng 888

8H0 8HO H ¾- | H ng-t 188

8H0 8HO H H ng-xi 988

8H0 8HO H ¾-ϊ H 388

SHO 8HO H -ΐ H Ψ

ΒΗΟ 8HO H H 888

8HO 8HO H -ΐ H 8HO Z 2

8HO SHO H H H 188

8HO 8HO gHO SHI 088

8HO 8HO 3a QZ

SHO gHO l k> 28

8HO 8HO 8HO

 SHO 8HO 8HO ng-u Z2

SHO 8HO 8HO Z

8HO 8HO 8HO ia 828

8HO 8HO 8HO ZZ2

SHO 8HO gHO a gHO IZ

GHO 8HO 8HO H 0Z2,

 SHO 8HO SHO 8HO qd 8X8

8HO SHO 8HO 8HO T02HO LI8

SHO 8HO gHO a 8HO ng 9T8

8HO 8HO SHO SHO SX8

8HO 8HO SHO SHO ng-n

 8HO 8HO 8HO 8HO -ΐ 818

8HO 8HD 8HO a SHO Z12

SHO 8HO SHO SHO Π8

SHO SHO 8HO 8HO 8HO 018

SHO 8HO 8HO a SHO H 608

 8HO SHO 8HO H m LOS

8HO 8HO SHO H 10SHO 90S

8HO 8HO 8HO H 908

SHO SHO SHO H Ψ02

8HO 8HO 8HO H 80S

SHO SHO 8HO H Z0

8HO SHO 8HO H X08

9H 9H zn

8

0iIC0 / T0df / X3d 66Τ6 ./Ϊ0 OAV Table 1-1 8

 No. Rl R2 R3 R4 R5 R6

351 'P CH3 i-Pr H CH3 CH3

352 TMS CH3 i-Pr H CH3 CH3

353 H Et i-Pr H CH3 CH3

354 CH3 Et i-Pr H CH3 CH3

'355 Et Et i-Pr H CH3 CH3

356 n-Pr Et i-Pr H CH3 CH3

357 i-Pr Et i-Pr H CH3 CH3

358 n-B Et i-Pr H CH3 CH3

359 i-B Et i-Pr H CH3 CH3

360 t-Bu Et i-Pr H CH3 CH3

361 CH2C1 Et i-Pr H CH3 CH3

362 Ph Et i-Pr H CH3 CH3

363 TMS Et i-Pr H CH3 CH3

364 H Hi-Pr CH3 CH3 CH3

365 CH3 H i-Pr CH3 CH3 CH3

366 Et Hi-Pr CH3 CH3 CH3

367 n-Pr H i-Pr CH3 CH3 CH3

368 i-Pr H i-Pr CH3 CH3 CH3

369 n-Bu H i-Pr CH3 CH3 CH3

370 i-Bu H i-Pr CH3 CH3 CH3

371 t-Bu Hi-Pr CH3 CH3 CH3

372 CH2C1 Hi i-Pr CH3 CH3 CH3

373 Ph Hi-Pr CH3 CH3 CH3

374 TMS Hi-Pr. CH3 CH3 CH3

375 H CH3 i-Pr CH3 CH3 CH3

376 CH3 CH3 i-Pr CH3 CH3 CH3

377 Et CH3 i-Pr CH3 CH3 CH3

378 n-Pr CH3 i-Pr CH3 CH3 CH3

379 i-Pr CH3 i-Pr CH3 CH3 CH3

380 n-Bu CH3 i-Pr CH3 CH3 CH3

381 i-Bu CH3 i-Pr CH3 CH3 CH3

382 t-Bu CH3 i-Pr CH3 CH3 CH3

383 CH2C1. CH3 i-Pr CH3 CH3 CH3

384 Ph CH3 i-Pr CH3 CH3 CH3

'' 385 TMS CH3 i-Pr CH3 CH3 CH3

386 H Et i-Pr CH3 CH3 CH3

387 CH3 Et i-Pr CH3 CH3 CH3

388 Et Et i-Pr CH3 CH3 CH3

389 n-Pr Et i-Pr CH3 CH3 CH3

390 i-Pr Et i-Pr CH3 CH3 CH3

391 n-Bu Et i-Pr CH3 CH3 CH3

392 i-Bu Et i-Pr CH3 CH3 CH3

393 t-Bu Et i-Pr CH3 CH3 CH3

394 CH2C1 Et i-Pr CH3 CH3 CH3

395 Ph Et i-Pr CH3 CH3 CH3

396 TMS Et i-Pr CH3 CH3 CH3

397 H H CH3 H Et H

398 CH3 H CH3 H Et H

399 Et H CH3 H Et H

400 n-Pr H CH3 H Et H H 8H0 8H0 8HO d 09f

H 8H0 8H0 8HO 10SHO 6 f

H Ά 8H0 8H0 8HO ng4 Sf

H 8H0 8H0 8HO m

H 8H0 8H0 8HO ng-u

 H 8H0 8H0 8HO

 H 8H0 SHO 8HO

 H 8H0 8HO 8HO 2ff

H 8H0 8H0 8HO 8HO Zff

H 8H0 8H0 8HO H Iff

H a 8H0 8H0 H Off

H 8H0 8HO H 62f

H 8H0 8HO H TOSHO 88 ^

H 8H0 8HO H L2f

H 8H0 8HO H 92f

H SHO 8HO H

 H 8H0 SHO 'H ¾-ΐ

 H 8H0 8HO H

 H 8H0 8HO H

 H SHO 8HO H 8HO τε ^

H SHO SHO H H 02f

H H 8H0 S GZf

H H 8H0 m SZf

H H SHO 10SHO LZ

H H 8HO 9Z

H H 8HO 9Zf

H H 8HO fZf

H H 8HO 2Z

H H 8HO ZZf

H H SHO IZf

H H 8HO εΗθ OZf

H H SHO H Glf

H H 8HO 8HO SHI 8T ^

H H 8HO 8HO m Llf

H H 8HO SHO DSHD 9lf

H H 8HO 8HO 9lf

H H 8HO SHO .flf

H H 8HO 8HO S

H H 8HO 8HO ¾-ϊ ZTf

H H 8HO 8HO llf

H H 8HO 8HO Olf

H H 8HO 8HO SHO

 H H SHO SHO H ■

H H 8HO H SHX LOf

H H 8HO H qdt dOf

H H 6HO H 10SHO 90f

HH 8HO H ⁿ a4 fOf

H ¾a H 8HO H 20f

 H H 8HO H ¾-ϊ lOf

9H SH zn TH "ON

 &-

OS

OZUO / lOdTIlDd 66T6Z, / 10 OAV Table 1 1 0

 No. Rl R2 R3 R4 R5 R6

451 TMS CH3 CH3 CH3 Et H

452 H Et CH3 CH3 Et H

453 CH3 EtCH3 CH3 Et H

454 Et Et CH3 CH3 Et H

455 Et CH3 CH3 Et H

456 ip _r Et CH3 CH3 Et H

457 n-Bu Et CH3 CH3 Et H

458 i-Bu Et CH3 CH3 Et H

459 t-B Et CH3 CH3 Et H

460 CH2C1 Et CH3 CH3 Et H

461 Ph. Et CH3CH3 Et H

 TMS Et CH3 CH3 Et H

H H H Et H

464 CH3 H Et H 'Et H

 H Et H Et H

H H Et H

Λ η H Et H

 H Et H

H Et H

4.70 H Et H

471 CH201 H H Et H .7 H Et H ¾ H F H Et H

474 "Rf H Et H

 H Et H

476 Et CH3 Et H Et H

477 _η -Ρτ CH3 Et H Et H

478 ip _r CH3 Et H Et H

479 CH3 Et H Et H

480 iB _u CH3 Et H Et H

481 t-Bu CH3 Et H Et H

482 CH2C1 CH3 Et H Et H

483 P CH3 Et H Et H

484 TMS CH3 Et H Et H

485 H Et Et H Et H

486 CH3 Et Et H Et H

487 Et Et Et H Et H

488 n_Pr Et Et H Et H

489 i-Pr Et Et H Et H

490 n-Bu Et Et H Et H

491 i-Bu Et Et H Et H

492 t-Bu Et Et H Et H

493 CH2C1 Et Et H Et H

494 Ph Et Et H Et H

495 TMS Et Et H Et H

496 H H Et CH3 Et H

497 CH3 H Et CH3 Et H

498 Et H Et CH3 Et H

499 n-Pr H Et CH3 Et H

500 i-Pr H Et CH3 Et H HH 8H0 SMJL 039

H H 8H0 6 9

H H 8H0 IOSHO Sf

H H 8H0 ng LfQ

H * a H. 8H0 9 9

H H 8H0

 H H 8H0 -ΐ both

H H SHO

H H SHO ΖΨ

H H -ϊ 8HO SHO TfQ

H H SHO H o ^ s

H H H 683

H H H qj 889

H H H ΤΟδΗΟ 2,88

H H H g 98S

H H H S89

H H H

H H H ¾-i ggg

H H H JJ-n Z2

H H H X8Q

H H H 9HO OSS

H H H H QZ9

H 8H0 a SHiL 8Z9

H 9H0 qj LZ2

H 8H0 10SHO QZ9

H 8H0 ng QZ9

H 8H0 ng-T ΨΖ9

H 8H0 ng-n SZ

H 8H0 -ΐ ZZ9

H 8H0 a IZ

H 8H0 0Z

H a 8H0 SHO 6T9

H 8H0 H 8IQ

H 8H0 SHO L19

H a 8H0 8HO 9TS

H 8H0 8HO lOZHD 9T9

H 8H0 8HO ng flQ

H 8H0 8HO ng-x 8IS

H 9H0 a 8HO ng-tc Z1

H a 9H0 8HO ¾-ΐ Π9

H a 8H0 8HO OTS

H 8H0 8HO 60S

H ¾ 8H0 SHO 8HO 80S

H 8H0 8HO H L09

H 8H0 H SHI 909

H 8H0H Qd SOS

H a '8H0 H TOSHO W9

H 8H0 H 80S

H 8H0 H Z09

H 8H0 H 109

9Ή. 9H 8H ΖΉ. TH "ON

 ι τ-im

 Z9

ZU0 / l0d £ / 13d 66Ϊ6Ζ. / Ϊ0 OAV Table 1 1 2

 No. Rl R2 R3 R4 R5 R6

551 H Et i-Pr H Et H

552 CH3 Et i-Pr H Et H

553 Et Et i-Pr H Et H

554 n-Pr Et i-Pr H Et H

555 i-Pr Et i-Pr H Et H

556 n-Bu Et i-Pr H Et H

557 i-Bu Et i-Pr H Et H

558 t-Bu Et i-Pr H Et H

559 CH2C1 Et i-Pr H EtH

560 Ph Et i-Pr H Et H

561 TMS Et i-Pr H Et H

562 H H i-Pr CH3 'Et H

563 CH3 H i-Pr CH3 Et H

564 Et H i-Pr CH3 Et H

565 n ^_ Pr H i-Pr CH3 Et H

566 i-Pr H i-Pr CH3 Et H

567 n-Bu H i-Pr CH3 Et H

568 i-Bu H i-Pr GH3 Et H

569 t-Bu H i-Pr CH3 Et H

570 CH2C1 H i-Pr CH3 Et H

571 Ph H i-Pr CH3 Et H

572 TMS Hi i-Pr CH3 Et H

573 H CH3 i-Pr CH3 Et H

574 CH3 CH3 i-Pr CH3 Et H

575 Et CH3 i-Pr CH3 Et H

576 n-Pr CH3 i-Pr CH3 Et H

577 i-Pr CH3 i-Pr CH3 Et H

578 n-Bu CH3 i-Pr CH3 Et H

579 i-Bu CH3 i-Pr CH3 Et H

580 t-Bu CH3 i-Pr CH3 Et H

581 CH2C1 CH3 i-Pr CH3 Et H

582 Ph CH3 i-Pr CH3 Et H

583 TMS CH3 i-Pr CH3 Et H

584 H Et i-Pr CH3 Et H

585 CH3 Et i-Pr CH3 Et H

586 Et Et i-Pr CH3 Et H

587 n-Pr Et i-Pr CH3 Et H

588 i-Pr Et i-Pr CH3 Et H

589 n-Bu Et i-Pr CH3 Et H

590 i-Bu Et i-Pr CH3 Et H

591 t-Bu Et i-Pr CH3 Et H

592 CH2C1 Et i-Pr CH3 Et H

593 Ph Et i-Pr CH3 Et H

594 TMS Et i-Pr CH3 Et H

595 H H CH3 H Et CH3

596 CH3 H CH3 H Et-CH3

597 Et H CH3 H Et CH3

598 n-Pr H CH3 H Et CH3

599 i-Pr H CH3 H Et CH3

600 n-Bu H CH3 H Et CH3 8H0 8HO 8HO H 0S9 εΗθ SHO 8HO 8HO 6 9

8ΗΟ 8HO 8HO 8HO Sfd

SHO 8HO 8HO 8HO 10SHO LW

6ΗΟ 8HO 8HO 8HO 9 ^ 9

8ΗΟ 8HO 8HO 8HO 9 9

8ΗΟ 8HO 8HO 8HO ng-u 9

8ΗΟ 8HO 8HO 8HO 8t9

8ΗΟ * a 8HO SHO SHO Zt9

8ΗΟ 8HO 8HO 8HO T 9

8ΗΟ a SHO 8HO 8HO SHO 0 9

8ΗΟ 8HO 8HO 8HO H 689

8ΗΟ 8HO 8HO H S phoenix 889

8ΗΟ 8HO SHO H m L2d

8ΗΟ 8HO 8HO H IOSHO 989

8ΗΟ 8HO 8HO H 989

8ΗΟ SHO 8HO H S9

8ΗΟ a 8HO 8HO H ng-u 889

8ΗΟ 8HO 8HO H S89

8ΗΟ 8HO 8HO H T89

8ΗΟ 8HO 8HO H 089

8ΗΟ a 8HO 8HO H 8HO 629

SHO 8HO 8HO H H 829

8ΗΟ H 8HO SHX LZd

SHO H 8HO ^ d 9Z9

8ΗΟ a H SHO TOSHO 9Z9

8ΗΟ H 8HO ng4 ΨΖ9

SHO H 8HO Z2

8HO H 8HO ng-u ZZd

8HO H 8HO ¾-ΐ IZd

8HO H 8HO 0Z9

8HO H 8HO 619

8HO a H 8HO SHO 819

8HO H 8HO H Lid

8HO H 8HO 8HO SHX 9T9

8HO H SHO 8HO m SI9

8HO a H 8HO 8HO ΌΖΉ.0

 8HO H 8HO 8HO 8T9

SHO H SHO 8HO ΖΪ9

8HO H 8HO 8HO TT9

8HO H SHO 8HO 019

8HO a H 8HO 8HO 609

SHO H 8HO 8HO 809

8HO a H 8HO 8HO SHO LOd

8HO H 8HO 8HO H 909

8HO H 8HO H S1ALL S09

8HO H 8HO H W9

8HO H 8HO H Ϊ02ΗΟ 809

8HO H 8HO H S09

SHO a H 8HO H T09

9H 8H zn • ° N ε i— 挲 τ 绻

0ZTC0 / I0df / X3d 66Ϊ6 ./Ϊ0 OAV Table 1 1 4

 No. Rl R2 R3 R4 R5 R6

651 CH3 Et CH3 CH3 Et CH3

652 Et Et CH3 CH3 Et CH3

653 n-Pr Et CH3 CH3 Et CH3

654 i-Pr Et CH3 CH3 Et CH3

655 n-Bu Et CH3 CH3 Et CH3

656 i-Bu Et .CH3 CH3 Et CH3

657 t-B Et CH3 CH3 Et CH3

658 CH2C1 Et CH3 CH3 Et CH3

659 Ph Et CH3 CH3 Et CH3

660 TMS Et CH3 CH3 Et CH3

661 H H Et H Et CH3

662 CH3 H Et H Et CH3

663 Et H Et H Et. CH3

664 n-Pr H Et H Et CH3

665 i-Pr H Et H Et CH3

666 n-Bu H Et H Et CH3

667 i-Bu H Et H Et CH3

668 t-Bu H Et H Et CH3

669 CH2C1 H Et 'H Et CH3

670 Ph H Et H Et CH3

671 TMS H Et H Et CH3

672 H CH3 Et H Et CH3

673 CH3 CH3 Et H Et CH3

674 Et CH3 Et H Et CH3

675 n-Pr CH3 Et H Et CH3

676 i-Pr CH3 Et H Et CH3

677 n-Bu CH3 Et H Et CH3

678 i-Bu CH3 Et H Et CH3

679 t-Bu CH3 Et H Et CH3

680 CH2C1 CH3 Et H Et CH3

681 Ph CH3 Et H Et CH3

682 TMS CH3 Et H Et CH3

683 H Et Et H Et CH3

684 CH3 Et Et H Et CH3

685 Et Et Et H Et GH3

686 n-Pr Et Et H Et CH3

687 i-Pr Et Et H Et CH3

688 n-Bu Et Et H Et CH3.

689 i-Bu Et Et H Et CH3

690 t-Bu Et Et H Et CH3

691 CH2C1 Et Et H Et CH3

692 Ph Et Et H Et CH3

693 TMS Et Et H Et CH3

694 H H Et CH3 Et CH3

695 CH3 H Et CH3 Et CH3

696 Et H Et CH3 Et CH3

697 n-Pr H Et CH3 Et CH3

698 i-Pr H Et CH3 Et CH3

699 n-Bu H Et CH3 Et CH3

700 i-Bu H Et CH3 Et CH3 No :! Table—1 5

 No. Rl R2 R3 R4 R5 R6

701 t-Bu H Et CH3 Et CH3

702 CH2C1 H Et CH3 Et CH3

703 Ph H Et CH3 Et CH3

704 TMS H Et CH3 Et CH3

705 H CH3 Et GH3 Et CH3

706 CH3 CH3 Et CH3 Et CH3

707 Et CH3 Et CH3 Et CH3

708 n—Pr CH3 Et CH3 Et CH3

709 i-Pr CH3 Et CH3 Et CH3

710 n-Bu CH3 Et CH3 Et CH3

711 i-Bu CH3 Et CH3 Et CH3

CH3 Et CH3

 714 Ph CH3 Et CH3 Et CH3

 TMS u CH3 Et CH3

71 fi CH3 Et CH3

 CH3 u

 71 Q n-* ΡτEt CH3

720 Pit Et

 721 τι -1 = ¾π "R ten CH3 Et CH3

722 Et CH3 t- "Rn Et CH3

724 CH2C1 Et CH3 Et CH3

725 CH3 Et CH3

726 TMS Et Et CH3 Et CH3

727 H i-Pr H Et CH3

728 CH3 H i-Pr H Et CH3

729 Et H i-Pr H Et CH3

730 H i-Pr H Et CH3

731 ip _r H i-Pr H Et CH3

732 n-Bu H i-Pr H Et CH3

733 x-Bu H ip _r H Et CH3

734 t-Bu H ip _r H Et CH3

735 CH2C1 H ip _r H Et CH3

736 Ph H ip _r H Et CH3

737 TMS Hi-Pr H Et CH3

738 H CH3 i-Pr H Et CH3

739 CH3 CH3 i-Pr H Et CH3

740 Et CH3 i-Pr H Et CH3

741 n-Pr CH3 i-Pr H Et 'CH3

742 i-Pr CH3 i-Pr H Et CH3

743 n-Bu CH3 i-Pr H Et CH3

744 i-Bu CH3 i-Pr H Et CH3

745 t-Bu CH3 i-Pr H Et CH3

746 CH2C1 CH3 i-Pr H Et CH3.

747 Ph CH3 i-Pr H Et CH3

748 TMS CH3 i-Pr H Et CH3

749 H Et i-Pr H Et CH3

750 CH3 Et i-Pr H Et CH3 Table 1 1 6

 No. Rl R2 R3 R4 R5 R6

751 Et Et i-Pr H Et CH3

752 n-Pr Et i-Pr H Et CH3

753 i-Pr Et i-Pr H Et CH3

754 n-B Et i-Pr H Et CH3

755 i-Bu Et i-Pr H Et CH3

756 t-Bu Et i-Pr H Et CH3

757 CH2C1 Et i-Pr H Et CH3

758 Ph Et i-Pr H Et CH3

759 TMS Et i-Pr H Et CH3

760 H H i-Pr CH3 Et CH3

761 CH3 H i-Pr CH3 Et CH3

762 Et Hi-Pr CH3 Et CH3

763 n-Pr H i-Pr CH3 Et CH3

764 i-Pr H i-Pr CH3 Et CH3

765 n-Bu Hi-Pr CH3 Et CH3

766 i-Bu H i-Pr CH3 Et CH3

767 t-Bu H i-Pr CH3 Et CH3

768 CH2C1 Hi-Pr CH3 Et CH3

769 Ph Hi-Pr CH3 Et CH3

770 TMS Hi-Pr CH3 Et CH3

771 H CH3 i-Pr CH3 Et CH3

7.72 CH3 CH3 i-Pr CH3 Et CH3

773 Et CH3 i-Pr CH3 Et CH3

774 n-Pr CH3 i-Pr CH3 Et CH3

775 i-Pr CH3 i-Pr CH3 Et CH3

776 n-Bu CH3 i-Pr CH3 Et CH3

777 i-Bu CH3 i-Pr CH3 Et CH3

778 t-Bu CH3 i-Pr CH3 Et CH3

779 CH2C1 CH3 i-Pr CH3 Et CH3

780 Ph CH3 i-Pr CH3 Et CH3

781 TMS CH3 i-Pr CH3 Et CH3

782 H Et 'i-Pr CH3 Et CH3

783 CH3 Et i-Pr CH3 Et CH3

784 Et Et i-Pr CH3 Et CH3

785 n-Pr Et i-Pr CH3 Et CH3

786 i-Pr Et i-Pr CH3 Et CH3

787 n-Bu Et i-Pr CH3 Et CH3

788 i-Bu Et i-Pr CH3 Et CH3

789 t-Bu Et i-Pr CH3 Et CH3

790 CH2C1 Et i-Pr CH3 Et CH3

791 Ph Et i-Pr CH3 Et CH3

792 TMS Et i-Pr CH3 Et CH3

793 H H CH3 H CI H

794 CH3 H CH3 H CI H

795 Et H CH3 H CI H

796 n-Pr H CH3 H CI H

797 i-Pr H CH3 H CI H

798 n-Bu H CH3 H CI H

799 i-Bu H CH3 H CI H

800 t-Bu H CH3 H CI H Table 1 1 7

 No. Rl R2 R3 R4 R5 R6

801 CH2C1 H CH3 H CI H

802 Ph H CH3 H CI H

803 TMS H CH3 H CI H

804 H CH3 CH3 H CI H

805 CH3 CH3 CH3 H CI H

806 Et CH3 CH3 H CI H

807 n-Pr CH3 CH3 H CI H

808 i-Pr CH3 CH3 H CI H

809 n-B CH3 CH3 H CI H

810 i-Bu CH3 CH3 H CI H

811 t-Bu CH3 CH3 H CI H

812 CH2C1 CH3 CH3 H CI H

813 Ph CH3 CH3 H CI H

814 TMS CH3 CH3 H CI H

815 H Et CH3 H CI H

816 CH3 Et CH3 H CI H

817 Et Et CH3 H CI H

818 n-Pr Et CH3 H CI H

819 i-Pr Et CH3 H CI

 820 n-Bu Et CH3 H CI H

821 i-Bu Et CH3 H CI H.

822 t-Bu Et CH3 H CI H

823 CH2C1 Et CH3 H CI H

824 Ph Et CH3 H CI H

825 TMS Et CH3 H CI H

826 H H CH3 CH3 CI H

827 CH3 H CH3 CH3 CI H

828 Et H CH3 CH3 CI H

829 n-Pr H CH3 CH3 CI H

830 i-Pr H CH3 CH3 CI H

831 n-Bu H CH3 CH3 CI H

832 i-Bu H CH3 CH3 CI H

833 t-Bu H CH3 CH3 CI H

834 CH2C1 H CH3 CH3 CI H

835 Ph H CH3 CH3 CI H

836 TMS H CH3 CH3 CI H

837 H CH3 CH3 CH3 CI H

838 CH3 CH3 CH3 CH3 CI H

839 Et CH3 CH3 CH3 CI H

840 n-Pr CH3 CH3 CH3 CI H

841 i-Pr CH3 CH3 CH3 CI H

842 n-Bu CH3 CH3 CH3 CI H

843 i-Bu CH3 CH3 CH3 CI H

844 t-Bu CH3 CH3 CH3 CI H

845 CH2C1 CH3 CH3 CH3 CI H

846 Ph CH3 CH3 CH3 CI H

847 TMS CH3 CH3 CH3 CI H

848 H Et CH3 CH3 CI H

849 CH3 Et CH3 CH3 CI H

850 Et Et CH3 CH3 CI H Table 1—18

 No. Rl R2 R3 R4 R5 R6

851 n-Pr Et CH3 CH3 CI H

852 i-Pr Et CH3 CH3 CI H

853 n-Bu Et CH3 CH3 CI H

854 i-Bu Et CH3 CH3 CI H

855 t-Bu Et CH3 CH3 CI H

856 CH2C1 Et CH3 CH3 CI H

857 Ph Et CH3 CH3 CI H

858 TMS Et CH3 CH3 CI H

859 H H Et H CI H

860 CH3 H Et H CI H

861 Et H Et H CI H

862 n-Pr H Et H CI H

863 i-Pr H Et H CI H

864 n-Bu H Et H CI H

865 i-Bu H Et H CI H

866 t-Bu H Et H CI H

867 CH2C1 H Et H CI H

868 Ph. H Et H CI H

869. TMS H Et H CI H

870 H CH3 Et H CI H

871 CH3 CH3 Et H CI H

872 Et CH3 Et H CI H

873 n-Pr CH3 Et H CI H

874 i-Pr CH3 Et H CI H

875 n-Bu CH3 Et H CI H

876 i-Bu CH3 Et H CI H

877 t-Bu CH3 Et H CI H

878 CH2C1 CH3 Et H CI H.

879 Ph CH3 Et H CI H

880 TMS CH3 Et H CI H

881 H Et Et H CI H

882 CH3 Et Et H CI H

883 Et Et Et H CI H

884 n-Pr Et Et H CI H

885 i-Pr Et Et H CI H

886 n-Bu Et Et H CI H

887 i-Bu Et Et H CI H

888 t-Bu Et Et H CI H

889 CH2C1 Et Et H CI H

890 Ph Et Et H CI H

891 TMS Et Et H CI H

892 H H Et CH3 CI H

893 CH3 H Et CH3 CI H

894 Et H Et CH3 CI H

895 n-Pr H Et CH3 CI .H

896 i-Pr H Et CH3 CI H

897 n-Bu H Et CH3 CI H

898 i-Bu H Et CH3 CI H

899 t-Bu H Et CH3 CI H

900 CH2C1 H Et CH3 CI H Table 1 1 9

 No. Rl R2 R3 R4 R5 R6

901 Ph H Et CH3 CI H

902 TMS H Et CH3 CI H

903 H CH3 Et CH3 CI H

904 CH3 CH3 Et CH3 CI H

905 Et CH3 Et CH3 CI H

906 n-Pr CH3 Et CH3 CI H

907 i-Pr CH3 Et CH3 CI H

908 n-B CH3 Et CH3 CI H

909 i-Bu CH3 Et CH3 CI H

910 t-Bu CH3 Et CH3 CI H

911 CH2C1 CH3 Et CH3 CI H

912 Ph CH3 Et CH3 CI H

913 TMS CH3 Et CH3 CI H

914 H Et Et CH3 CI H

915 CH3, Et Et CH3 CI H

916 Et Et Et CH3 CI H

917 n-Pr Et Et CH3 CI H

918 i-Pr Et Et CH3 CI H

919 n-Bu Et Et CH3 CI H

920 i-Bu Et Et CH3 CI H

921 t-Bu Et Et CH3 CI H

922 CH2C1 Et Et CH3 CI H

923 Ph Et Et CH3 CI H

924 TMS Et Et CH3 CI H

925 H H i-Pr H CI H

926 CH3 H i-Pr H CI H

927 Et H i-Pr H CI H

928 n-Pr H i-Pr H CI H

929 i-Pr H i-Pr H CI H

930 n-Bu H i-Pr H CI H

931 i-Bu H i-Pr H CI H

932 t-Bu H i-Pr H CI H

933 CH2C1 H i-Pr H CI H

934 Ph H i-Pr H CI H

935 TMS Hi-Pr H CI H

936 H CH3 i-Pr H CI H

937 CH3 CH3 i-Pr H CI H

938 Et CH3 i-Pr H CI H

939 n-Pr CH3 i-Pr H CI H

940 i-Pr CH3 i-Pr H CI H

941 n-Bu CH3 i-Pr H CI H

942 i-Bu CH3 i-Pr H CI H

943 t-Bu CH3 i-Pr H CI H

944 CH2C1 CH3 i-Pr H CI H

945 Ph CH3 i-Pr H CI H

946 TMS CH3 i-Pr H CI H

947 H Et i-Pr H CI H

948 CH3 Et i-Pr H CI H

949 Et Et i-Pr H CI H

950 n-Pr Et i-Pr H CI H Table 1—20

 No. Rl R2 R3 R4 R5 R6

951 i-Pr Et i-Pr H CI H

952 n-Bu Et i-Pr H CI H

953 i-Bu Et i-Pr H CI H

954 t-Bu Et i-Pr H CI H

955 CH2C1 Eti-Pr H ci H

956 Ph Et i-Pr H CI H

957 TMS Et i-Pr H CI H

958 H H i-Pr CH3 CI H

959 CH3 H i-Pr CH3 CI H

960 Et H i-Pr CH3 CI H

961 n-Pr H i-Pr CH3 CI H

962 i-Pr H i-Pr CH3 CI H

963 n-Bu H i-Pr CH3 CI H

964 i-Bu H i-Pr CH3 CI H

965 t-Bu H .i-Pr CH3 CI H

966. CH2C1 H i-Pr CH3 CI H

967 Ph H i-Pr CH3 CI H

968 TMS H i-Pr CH3 CI H

969 H CH3 i-Pr CH3 CI H

970 CH3 CH3 i-Pr CH3 CI H

971 Et CH3 i-Pr CH3 CI H

972 n-Pr CH3 i-Pr CH3 CI H

973 i-Pr CH3 i-Pr CH3 CI H

974 n-Bu CH3 i-Pr CH3 CI H

975 i-Bu CH3 i-Pr CH3 CI H

976 t-Bu GH3 i-Pr CH3 CI H

977 CH2C1 CH3 i-Pr CH3 CI H

978 Ph CH3 i-Pr CH3 CI H

979 TMS CH3 i-Pr CH3 CI H

980 H Et i-Pr CH3 CI H

981 CH3 Et i-Pr CH3 CI H

982 Et Et i-Pr CH3 CI H

983 n-Pr Et i-Pr CH3 CI H

984 i-Pr Et i-Pr CH3 CI H

985 n-Bu Et i-Pr CH3 CI H

986 i-Bu Et i-Pr CH3 CI H

987 t-Bu Et i-Pr CH3 CI H

988 CH2C1 Et i-Pr CH3 CI H

989 Ph Et i-Pr CH3 CI H

990 TMS Et i-Pr CH3 CI H

991 H H CH3 H CI CH3

992 CH3 H CH3 H CI CH3

993 Et H CH3 H CI CH3

994 n-Pr H CH3 H CI CH3

995 i-Pr H CH3 H CI CH3

996 n-Bu H CH3 H CI CH3

997 i-Bu H CH3 H CI CH3

998 t-Bu H CH3 H CI CH3

999 CH2C1 H CH3 H CI CH3

1000 Ph H CH3 H CI CH3 Table 1 I 2

 No. Rl R2 R3 R4 R5 R6.

1001 TMS H CH3 H CI CH3

1002 H CH3 CH3 H CI CH3

1003 CH3 CH3 CH3 H CI CH3

1004 Et CH3 CH3 H CI CH3

1005 n-Pr CH3 CH3 H CI CH3

1006 i-Pr CH3 CH3 H CI CH3

1007 n-Bu CH3 CH3 H CI CH3

1008 i-Bu CH3 CH3 H CI CH3

1009 t-Bu CH3 CH3 H CI CH3

1010 CH2C1 CH3 CH3 H CI CH3

1011 Ph CH3 CH3 H CI CH3

1012 TMS CH3 CH3 H CI CH3

1013 H Et CH3 H CI CH3

1014 CH3 Et CH3 H CI CH3

1015 Et Et CH3 H CI CH3

1016 n-Pr Et CH3 H CI CH3

1017 i-Pr Et CH3 H CI CH3

1018 n-Bu Et CH3 H CI CH3

1019 i-Bu Et CH3 H CI CH3

1020 t-Bu Et CH3 H CI CH3

1021 CH2C1 Et CH3 H CI CH3

1022 Ph Et CH3 H CI CH3

1023 TMS Et CH3 H CI CH3

1024 H H CH3 CH3 CI CH3

1025 CH3 H CH3 CH3 CI CH3

1026 Et H CH3 CH3 CI CH3

1027 n-Pr H CH3 CH3 CI CH3

1028 i-Pr H CH3 CH3 CI CH3

1029 n-Bu H CH3 CH3 CI CH3

1030 i-Bu H CH3 CH3 CI CH3

1031 t-Bu H CH3 CH3 CI CH3

1032 CH2C1 H CH3 CH3 CI CH3

1033 Ph H CH3 CH3 CI CH3

1034 TMS H CH3 CH3 CI CH3

1035 H CH3 CH3 CH3 CI CH3

1036 CH3 CH3 CH3 CH3 CI CH3

1037 Et CH3 CH3 CH3 CI CH3

1038 n-Pr CH3 CH3 CH3 CI CH3

1039 i-Pr CH3 CH3 CH3 CI CH3

1040 n-Bu CH3 CH3 CH3 CI CH3

1041 i-Bu CH3 CH3 CH3 CI CH3

1042 t-Bu CH3 CH3 CH3 CI CH3

1043 CH2C1 CH3 CH3 CH3 CI CH3

1044 Ph CH3 CH3 CH3 CI CH3

1045 TMS CH3 CH3 CH3 CI CH3

1046 H Et CH3 CH3 CI CH3

1047 CH3 Et CH3 CH3 CI CH3

1048 Et Et CH3 CH3 CI CH3

1049 n-Pr Et CH3 CH3 CI CH3

1050 i-Pr Et CH3 CH3 CI GH3

8H0 10 Η OSTT

8H0 TO Η -ΐ 6tll

8H0 10 Η -ΐ sni

8H0 10 Η -ΐ m mi

SHO TO Η ¾-ϊ 9 U

8HO TO Η ¾-ΐ * a H 9ΨΙΙ

8HO 10 Η T-T SHO fll

8HO 10 Η ¾-ϊ 8H0 ^ d S I

8HO 10 Η ¾-ΐ SHO TOSHO zm

8HO 10 Η Μ-ΐ SHO mi

8HO 10 Η SHO O TT

8HO TO Η ¾-Ι 8H0 na-u 68ΙΪ

8HO 10 Η 8H0 88TT

8HO 10 Η ¾-ΐ SHO IT IT LBU

SHO 10 Η SHO 98TT

SHO ΐθ ¾ ¾-ΐ SHO 8H0 S8TI

SHO TO Η -ΐ SHO H ^ 8ΤΤ

8HO ID Η ¾-ΐ H 88TT

8HO 10 Η H ¾ S8TT

8HO 10 Η ¾-Τ H IOSHO τεπ

8HO 10 Η ¾-ϊ H οεττ

8HO 10 Η ¾-ΐ H 6STT

SHO 10 Η -ΐ H

 8HO 10 Η ¾-Ι H LZU

8HO 10 Η ¾-ϊ H 9ZU

8HO 10 Η ¾-ΐ H 95TT

8HO 10 Τ ¾H 8H0 ZU

8HO 10 Η. ¾-ϊ H H 2ZU

8HO ΐθ 8Η0 SHI ZZU

SHO ΐθ 8Η0 ^ d IZ

8HO 10 8Η0 ΌΖΉ.0 OZU

8H3 ΐθ 8Η0 6TTT

8HO 10 8Η0 8TTT

8HO 10 8Η0 Llll

8HO TO 8Η0 9TTT

SHO 10 8Η0 a STTT

SHO ΐ〇 8Η0 a mi

8HO ΐ〇 8Η0 8H0 8TIT

SHO 10 8Η0 H zm

8HO ΐθ 8Η0 8H0 SHI ΤΤΠ

8HO 10 8Η0 8H0 m OTTT

SHO 10 εΗΟ SHO DSHD 60TT

8HO 10 8Η0 SHO ng4 80TI

8HO 10 8Η0 SHO LOU

SHO ΐθ 8Η0 SHO ng-n 90TT

SHO 10 8Η0 8H0 -ΐ SOTT

8HO 10 8Η0 8H0 ton

SHO 10 8Η0 8H0 son

8HO ΐ〇 8Η0 8H0 8H0 zo

SHO ΪΟ 8Η0 8H0 H TOIT 9H SH 8H ZU mON

f9

orico / iodf / x3d 6616 /, / TO OAV οτ

Tf) ΟΤΛΤΤ, OOTT

 u / QTT

 G ιϋ TD RD QOTT

 Tf) ΐΐσ.α GQTT

 ησ a.τ ·

 Tf)

 Λ tt TQTT

 TO PHD ORTT

 u u PHD βλΤΤ

 Tf) τχ Q / TT

 TO 8Η) mi gHO TO 8H0 QUI

 8H0 TO 8H0 tig fill

• gHO ΐθ 8H0 JJ-τ 8H0 ng-i sin

 8H0 ΐθ 8H0 8H0 ng.n ZLll

 8H0 ΐθ 8H0 8H0 TATT

 8H0 10 8H0 ¾-ϊ SHO O TT

 8H0 ΪΟ 8H0 ¾-ϊ 8H0 69TT

 8H0 10 8H0 -ΐ 8H0 SHO 89TT

 8H0 ID 8H0 ¾-ΐ 8H0 H LdU

 8H0 TO 8H0 ¾-ΐ H SMI 99IT

 8H0 10 8H0 ¾-ϊ H ^ d S9IT

 8H0 10 8H0 H 10SH0 fQU

 8H0 ΐθ 8H0 H ng4 89TT

 8H0 10 8H0 ¾-ϊ H ng-ΐ S9TI

 8H0 ΐθ 8H0 H ng-u Τ9Π

 SHO 10 8H0 -ΐ H 09TI

 8H0 10 8H0 H 6STI

 8H0 10 8H0 H 8QIT

 SHO ΐθ 8H0 H 8H0 L9U

 SHO 10 8H0 H H 9SIT

 8H0 ΐθ H ¾-ΐ S1A [sen

 SHO ΐθ H -ΐ m

 8H0 ΐθ H -ΐ IDZBD 8SII

 8H0 ϊ〇 H Ζ ΤΪ

 8H0 10 H TSTT

 9H 3Ή 8Η in ON

29

orico / iodf / i3d 6616 /, / TO OAV Table 2

 Rl R2 R3 R4 R5 R6

H H CH3 H CH20 CH3 H

CH3 H CH3 H CH20 CH3 H

Et H CH3 H CH20CH3 H n-Pr H CH3 H CH20CH3 H i-Pr H CH3 H CH20CH3 H n-B H CH3 H CH20CH3 H i-B H CH3 H CH20CH3 H t-Bu H CH3 H CH20CH3 H

CH2C1 H CH3 H CH20 CH3 H

Ph H CH3 H CH20CH3 H

TMS H CH3 H CH20CH3 H

H CH3 CH3 H CH20CH3 H

CH3 CH3 CH3 H CH20CH3 H

Et CH3 CH3 H CH20CH3 H n-Pr CH3 CH3 H CH20CH3 H i-Pr CH3 CH3 H CH20CH3 H n-Bu CH3 CH3 H CH20CH3 H i-Bu CH3 CH3 H CH20CH3 H t-B CH3 CH3 H CH20CH3 H

CH2C1 CH3 CH3 H CH20CH3 H

Ph CH3 CH3 H CH20CH3 H

TMS CH3 CH3 H CH20CH3 H

H Et CH3 H CH20CH3 H

CH3 Et CH3 H CH20 CH3 H

Et Et CH3 H CH20CH3 H n-Pr Et CH3 H CH20CH3 H i-Pr Et CH3 H CH20CH3 H n-Bu Et CH3 H CH20CH3 "H i-Bu Et CH3 H CH20CH3 H t-Bu Et CH3 H CH20CH3 H

CH2C1 Et CH3 H CH20CH3 H

Ph Et CH3 H CH20CH3 H

TMS Et CH3 H CH20CH3 H

H H Et H CH20CH3 H

CH3 H Et H CH20 CH3 H

Et H Et H CH20CH3 H n-Pr H Et H CH20CH3 H i-Pr H Et H CH20CH3 H n-Bu H Et H CH20CH3 Hi i-Bu H Et H CH20CH3 H t-Bu H Et H CH20CH3 H

CH2C1 H Et H CH20CH3 H

Ph H Et H CH20CH3 H

TMS H Et H CH20CH3 H

H CH3 Et H CH20CH3 H

CH3 CH3 Et H CH20CH3 H

Et CH3 Et H CH20CH3 H n-Pr CH3 Et H CH20CH3 Hi-Pr CH3 Et H CH20CH3 H n-Bu CH3 Et H CH20CH3 H Table 2

 Rl R2 R3 R4 R5 R6 i-B CH3 Et H CH20CH3 H t-Bu CH3 Et H CH20CH3 H

CH2C1 CH3 Et H CH20CH3 H

Ph CH3 Et H CH20CH3 H

TMS CH3 Et H CH20CH3 H

H Et Et H CH20CH3 H

CH3 Et Et H CH20CH3 H

Et Et Et H CH20CH3 H n-Pr Et Et H CH20CH3 H i-Pr Et Et H CH20CH3 H n-Bu Et Et H CH20CH3 Hi i-Bu Et Et H CH20CH3 H t-Bu Et Et H CH20CH3 H

CH2C1 Et Et H CH20CH3 H

Ph Et Et H, CH20CH3 H

TMS Et Et H CH20CH3 H

H H i-Pr H CH20CH3 H

CH3 H i-Pr H CH20 CH3 H

Et H i-Pr H CH20CH3 H n-Pr H i-Pr H CH20CH3 H i-Pr H i-Pr H CH20CH3 H n-Bu H i-Pr H CH20CH3 H i-Bu H i-Pr H CH20CH3 H t- Bu H i-Pr H CH20CH3 H

CH2C1 H i-Pr H CH20CH3 H

Ph H i-Pr H CH20CH3 H

TMS Hi-Pr H CH20CH3 H

H CH3 i-Pr H CH20CH3 H

CH3 CH3 i-Pr H CH20CH3 H

Et CH3 i-Pr H CH20CH3 H n-Pr CH3 i-Pr H CH20CH3 H i-Pr CH3 i-Pr H CH20CH3 H n-Bu CH3 i-Pr H CH20CH3 Hi i-Bu CH3 i-Pr H CH20CH3 H t- Bu CH3-i-Pr H CH20CH3 H

CH2C1 CH3 i-Pr H CH20CH3 H

Ph CH3 i-Pr H CH20CH3 H

TMS CH3 i-Pr H CH20CH3 H

H Et i-Pr H CH20CH3 H

CH3 Et i-Pr H CH20CH3 H

Et Et i-Pr H CH20CH3 H n-Pr Et i-Pr H CH20CH3 H i-Pr Et i-Pr H CH20CH3 H n-Bu Et i-Pr H CH20CH3 H i-Bu Et i-Pr H CH20CH3 H t- Bu Et i-Pr H CH20CH3 H

CH2C1 Et i-Pr H CH20CH3 H

Ph Et i-Pr H CH20CH3 H

TMS Et i-Pr H CH20CH3 H

HH CH3 CH3 CH20CH3 H Η BD0ZHD 8H0 aT 09T ττ OTTO

 Η SHOOoHJ a O bTHTJ 6 I

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Η SHDOoHD a

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Η SHOOoHO SHO H L2l

Η SHOOSHO 8H0 + a H 98T

Η SHOOoHO SHO H S8T

Η SHOOSHO 8 HO 3 H 8H0 81

Η SHOOSHO 8H0 H H 88T

Η SHOOSHO 8H0 8H0 Z T

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Η 8H0OSH0 SHO SHO a 10SH0 08T

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Η 8H00SH0 SHO 8H0 LZl

Η 8H0OSH0 SHO 8H0 ¾-ϊ 9ZI

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Η 8H00SH0 8H0 SHO fZl

Η 8H00SH0 8H0 SHO a 8H0 ZI

Η 8H0OSHO SHO SHO 4a H ZZl

Η 8H00SH0 8H0 8H0 8H0 SHI 1ST

Η 8H0OSH0 SHO SHO SHO OZl

Η SHOOSHO SHO SHO TOSHO 6TT

Η SHDOSHD BHO SHO SHO ^N 9 8IT

Η SHOOoHO SHO 8H0 8H0 ^η 9 ΐ LIT

Η SHOOoHO SHO SHO SHO 9TT

Η SHOOoHO 8H0 STT

Η SHOOoHO SHO SHO 8H0 fll

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89

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H 8H00SH0 8HO 86T

H SHOOSHO 8HO L6l

H 8HOOSHO 8HO IOSHO 96T

H SHOOSHO 8HO S6T

H SHOOSHD 8HO & l

H 8HOOSHO 8HO ¾-ΐ 86T

 H 8HOOSHO 8HO Μ-ϊ T6T

H 8HOOSHO 8HO ¾-Τ a 06T

H 8HOOSHO 8HO SHO 68T

H 8HOOSHO 8HO * a H 88T

H 8ΗΟΟδΗΟ 8HO ¾-Τ 8HO LSI

H 8HOOSHO SHO ¾-ϊ 8HO 981

H 8HOOSHO 8HO. ¾-Τ 8HO Ϊ02ΗΟ S8I

H 8HOOSHO 8HO 8HO f l

H 8HOOSHO 6HO 6HO 88T

H 8HOOSHO 8HO SHO S8T

H 8HOOSHO 8HO ¾-? 8HO Ϊ8Τ

H SHOOSHO SHO ¾-ΐ 8HO 08T

H SHOOSHO 8HO ¾-ϊ 8HO 6LT

H 8HOOSHO SHO ¾-ΐ 8HO SHO 8LI

H SHOOSHO 8HO SHO H LLl

H 8HOOSHO 2Ή.0 H 9 I

H SHDOSHO 8HO ¾-? H S

H SHOOSHO 8HO H fLl

H 8HOOSHO SHO ¾-τ H 2LI

H 8HOOSHO 8HO H ZL \

H 8HOOSHO SHO ¾τ H III

H SHOOSHO 8HO H QUI

H 8HOOSHO 8HO -ΐ H 69T

H SHOOSHO 8HO Μ-ΐ H 891

H 8H002HO 8HO ¾-ϊ H 8HO L9X

H SHOOZHO 8HO -ΐ H H 991

H 8HOOSHO SHO Ϊ3 S9T

H moomo SHO Ϊ3 Ψ9Τ

H 8HOOSHO SHO TOSHO 891

H 8H003HO 8HO ¾ Z9l

H 8HOOSHO 8HO a T9T

H 8HOOSHO 8HO 091

H 8HOOSHO SHO 691

H 8HOOSHO SHO 8ST

H 8HOOSHO 8HO LSI

H 8H002HO 8HO SHO 9ST

H SHDOSHO 8HO H SST

H SH003HO 8HO 8HO SHI sx

H 8HOOSHO 8HO SHO 8ST

H 9HOOSHO SHO 8HO 10SHO SST

H 8HOOZHO SHO 8HO 19T

9H SH 8H zn TH

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OH〇§ S 〇 ΐδ Table 2-1

 No. Rl R2 3 R4 R5 R6

351 Ph CH3 Et CH3 CH20CH3 CH3

352 TMS CH3 Et CH3 CH20 CH3 CH3

353 H Et Et CH3 CH20CH3 CH3

354 CH3 Et Et CH3 CH20 CH3 CH3

355 Et Et Et CH3 CH20CH3 CH3

356 n-Pr Et Et CH3 CH20CH3 CH3

357 i-Pr Et Et CH3 CH20CH3 CH3

358 n-Bu Et Et CH3 CH20CH3 CH3

359 i-Bu Et Et CH3, CH20CH3 CH3

360 t-B Et Et CH3 CH20CH3 CH3

361 CH2C1 Et Et CH3 CH20CH3 CH3

362 Ph. Et Et CH3 CH20CH3 CH3

363 TMS Et Et CH3 CH20CH3 CH3

364 H H i-Pr CH3 CH20 CH3 CH3

365 CH3 H i-Pr CH3 CH20 CH3 CH3

366 Et Hi-Pr CH3 CH20 CH3 CH3

367 n-Pr H i-Pr CH3 CH20 CH3 CH3

368 i-Pr H i-Pr CH3 CH20 CH3 CH3

369 n-Bu Hi-Pr 0H3 CH20CH3 CH3

370 i-Bu H i-Pr CH3 CH20 CH3 CH3

371 t-Bu Hi-Pr CH3 CH20 CH3 CH3

372 CH2C1 Hi i-Pr CH3 CH20CH3 CH3

373 Ph Hi-Pr CH3 CH20 CH3 CH3

374 TMS Hi-Pr CH3 CH20 CH3 .CH3

375 H CH3 i-Pr CH3 CH20 CH3 CH3

376 CH3 CH3 i-Pr CH3 CH20 CH3 CH3

377 Et CH3 i-Pr CH3 CH20 CH3 CH3

378 n-Pr CH3 i-Pr CH3 CH20 CH3 CH3

379 i-Pr GH3 i-Pr CH3 CH20 CH3 CH3

380 n-Bu CH3 i-Pr CH3 CH20 CH3 CH3

381 i-Bu CH3 i-Pr CH3 CH20 CH3 CH3

382 t-Bu CH3 i-Pr CH3. CH20CH3 CH3

383 CH2C1 CH3 i-Pr CH3 CH20CH3 CH3

384 Ph CH3 i-Pr CH3 CH20 CH3 CH3

385 TMS CH3 i-Pr CH3 CH20 CH3 CH3

386 H Et i-Pr CH3 CH20 CH3 CH3

387. CH3 Et i-Pr CH3 CH20CH3 CH3

388 Et Et i-Pr CH3 CH20CH3 CH3

389 n-Pr Et i-Pr GH3 CH20CH3 CH3

390 i-Pr Et i-Pr CH3 CH20 CH3 CH3

391 n-Bu Et i-Pr CH3 CH20 CH3 CH3

392 i-Bu Et i-Pr CH3 CH20CH3 CH3

393 t-Bu Et i-Pr CH3 CH20CH3 CH3

394 CH2C1 Et i-Pr CH3 CH20CH3 CH3

395 Ph Et i-Pr CH3 CH20CH3 CH3

396 TMS Et i-Pr CH3 CH20CH3 CH3

397 H H CH3 H CH20CH2CH20CH3 H

398 CH3 H CH3 H CH20CH2CH20CH3 H

399 Et H CH3 H CH20CH2CH20CH3 H

400 n-Pr H .cm H CH20CH2CH20CH3 H CO

¾2 〇

C20C HCH20CH3H2 JP01 / 03120

76

 Table 2

 No. Rl R2 R3 R4 R5 R6

501 n-Bu H CH3 CH3 CH20CH2CH20CH3 H

502 i-B H CH3 CH3 CH20CH2CH20CH3 H

503 t-Bu H CH3 CH20 CH2CH20 CH3 H

504 CH2C1 H CH3 CH3 CH20CH2CH20CH3 H

505 Ph.H CH20 CH2CH20 CHS H

506 TMS H u tj CH20CH2CH20CH3 H

507 H CH3 CH3 (H3 CH20CH2CH20CH3 H

508 CH3 CH3 CHS v CH20CH2CH20CH3 H

509 Et CH3 i CH20CH2CH20CH3 H JL JL _n -p _r CH3 1 JJ CH20GR2CH20 H3

 511 i-P CHS tj V_ CH20CH2CH20CH8

 512 JUL JLJ ΠΗ2ΩΠΗ JL 2Γ, Η2ΩΠΗί ij¾

i-Ru ΠΗ2ΩΠΗ2Π ν_ Η ώ2ΩΠΗλ

i <JL ± 0 V JT υ TT

 V G ν ^ Ι TJ Ω Pit TJ

 JTl JC no

M \ ten v

Λ -VV li Πΰ Πΰ ~ 1 _ JT1 JT n ο T

 524 J_J u. J— 1 ΰ V_ _> 0

526 CH2C1 tj ΰ i t_ TT

 530 CH3 H j CH2O0H2CH2OOH

 531 Et H Et CH20 CH2CH20 CHS H

532 ii-p _r H Et GR20 GH2CH20 CH3 H

533 ip _r H Et CH2O0H2CH2OCHB

534 _n -Bu H Et CH20 CH2GH20 CHS JL

 536 t-Bu H Et CH3 CH20CH2CH20CH3 H

537 CH2C1 H Et CH3 CH20 CH2CH20 CH3 H

538 Ph.H Et CH3 CH20CH2CH20CH3 H

539 TMS H Et CH20CH2CH20CH3 H

540 H CH3 Et CH3 CH20CH2CH20CH3 H

541 CH3 CH3 Et CH3 CH20CH2CH20CH3 H

542 Et CH3 Et CH3 CH20CH2CH20CH3 H

543 n-Pr CH3 Et CH3 CH20CH2CH20CH3 H

544 i-Pr CH3 Et CH3 CH20CH2CH20CH3 H

545 n-Bu CH3 Et CH3 CH20CH2CH20CH3 H

546 i-Bu CH3 Et CH3 CH20CH2CH20CH3 H

547 t-Bu CH3 Et CH3 CH20CH2CH20CH3 H

548 CH2C1 CH3 Et CH3 CH20CH2CH20CH3 H

549 Ph CH3 Et CH3 CH20CH2CH20CH3 H

550 TMS CH3 Et CH3 CH20CH2CH20CH3 H H0 8H0OSH0SH0OSHO H SHO Η 009 H0 8H0OSH0SH0OSH0 H 8HO Η 663 H0 8H002HOSHOOSHO H 8HO Η 86S H0 8H003HOSHOOZHO H 8HO Η 169 H0 SHOO ^ HOSHOOSHO H 8HO Η 8HO 96OS H0HOS 96HO

H SHOOSHOSHOOSHO 8HO ¾-ΐ SJAI1 ^ 63

H 8HOOSHOSHOOSHO 8HO ^ d 86S

H 8HOOSHOSHOOSHO 8HO TOSHO Z69

H SHOOSHOSHOOSHO 8HO ¾-ϊ 163

H 8HOOSHOSHOOSHO 8HO 069

H 8HOOSHOSHOOSHO 8HO a 682

H 8HOOSHOSHOOSHO 8HO ¾ 88S

H 8HOOSHOSH002HO 8HO 83

H 8H002HOSHOOSHO 8HO ^ d- 98S

H SHOOSHOSHOOSHO 8HO ¾-ϊ 8HD 989

H 8HOOSHOSHOOSHO 8HO -ί H Lake

H SHOOSHOSHOOSHO SHO d-ΐ 8HO S1ALL 889

H SHOOSHOSHOOSHO 8HO ¾-ϊ SHO d ZS9

H 8HOOSHOSHOOSHO 8HO ^ d-T SHO IDZHD T8S

H 8H003HOSHOOSHO SH〇 ¾SHO ng4 089

H 8H003HOSHOOSHO 8HO 8HO 6L9

H 8HOOSHOSHOOSHO 8HO -ΐ 8HO SL9

H 8HOOSHOSHOOSHO 8HO ¾-ϊ 8HO LL9

H SHOOSHOSHOOSHO 8HO ¾-ϊ 8HO 9L9

H 8HOOSHOSHOOSHO 8HO 8HO 919

H 8HOOSHOSHOOSHO 8HO mo 8HO fL9

H 8HOOSH02HOOSHO 8HO 8HO H SL9

H 8HOOSHOSHOOSHO 8HO H SMJL ZL9

H SHOOSHOSHOOSHO SHO ¾ · Τ H ^ d 9

H 8HOOSHOSHOOZHO 8HO ¾-ΐ H ΌΖΉ.0 0L9

H 8HOOSHOSHOOSHO SHO ¾-ϊ H ng4 699

H SHOOS HOOSHO 8HO ¾ H 89S

H 8Η0ΟδΗ0δΗ0Ο2ΗΟ 2Ή.0 ¾-ΐ H ng-π L99

H 8HOOSHOSHOOSHO 8HO ¾-ϊ H 99S

H 8H0OSHOSH0O2HO 8HO -ΐ H S9S

H SHOOSHOSHOOSHO 8HO ¾-ΐ H 9S

H 8H0OSHOZH0O5H0 8HO H 8ΗΟ 89S

H 8HOOSHOSHOOSHO 8HO H Η S9S

H SHOOSHOSHOOSHO 8HO SHX T99

H 8HOOSH02H005HO SHO ¾i 099

H 8HOOSHOSHOOSHO 8HO DSHD 6SS

H 8HOOSHOSH002HO SHO a n 89S

H 8HOOSH02HOOSHO 8HO L99

H 8HOOSHOSHOOSHO 8HO ng-u 99S

H SHOOSH〇SHOO 〇 8HO -ΐ SS9

H 8HOOSHOSH005HO SHO SS

H 8H0OSH0SH0OSH3 8HO 8SS

H 8HOOZHOSHOOSHO 8HO SHO Z99

H 8HOOSHOSHOOSHO 8HO H TS9

9H 9H 8H zn T¾ "ON

∑IC0 / I0df / X3d 66Ϊ6 ./Ϊ0 OAV

Table 1 1 4

 No. Rl R2 R3 R4 R5 R6

651 CH3 Et Et H CH20CH2CH20CH3 CH3

652 Et Et Et H CH20CH2CH20CH3 CH3

653 n-Pr Et Et H CH20CH2CH20CH3 CH3

654 i-Pr Et Et H CH20CH2CH20CH3 CH3

655 n-B Et Et H CH20CH2CH20CH3 CH3

656 i-Bu Et Et H CH20CH2CH20CH3 CH3

657 t-Bu .Et Et H CH20CH2CH20CH3 CH3

658 CH2C1 Et Et H CH20CH2CH20CH3 CH3

659 Ph Et Et H CH20CH2CH20CH3 CH3

660 TMS Et Et H CH20CH2CH20CH3 CH3

661 H Hi-Pr H CH20CH2CH20CH3 CH3

662 CH3 Hi-Pr H CH20CH2CH20CH3 CH3

663 Et Hi-Pr H CH20CH2CH20CH3 GH3

664 n-Pr H i-Pr H CH20CH2CH20CH3 CH3

665 i-Pr H i-Pr H CH20CH2CH20CH3 CH3

666 n-Bu Hi-Pr H CH20CH2CH20CH3 CH3

667 i-Bu H i-Pr H CH20CH2CH20CH3 CH3

668 t-Bu Hi-Pr H CH20CH2CH20CH3 CH3

669 CH2C1 Hi i-Pr H CH20CH2CH20CH3 CH3

670 Ph Hi-Pr H CH20CH2CH20CH3 CH3

671 TMS Hi-Pr H CH20CH2CH20CH3 CH3

672 H CH3 i-Pr H CH20CH2CH20CH3 CH3

673 CH3 CH3 i-Pr H CH20CH2CH20CH3 CH3

674 Et CH3 i-Pr H CH20CH2CH20CH3 CH3

675 n-Pr CH3 i-Pr H CH20CH2CH20CH3 CH3

676 i-Pr CH3 i-Pr H CH20CH2CH20CH3 CH3

677 n-Bu CH3 i-Pr H CH20CH2CH20CH3 CH3

678 i-Bu CH3 i-Pr H CH20CH2CH20CH3 CH3

679 t-Bu CH3 i-Pr H CH20CH2CH20CH3 CH3

680 CH2C1 CH3 i-Pr H CH20CH2CH20CH3 CH3

681 Ph CH3 i-Pr H CH20CH2CH20CH3 CH3

682 TMS CH3 i-Pr H CH20CH2CH20CH3 CH3

683 H Et i-Pr H CH20CH2CH20CH3 CH3

684 CH3 Et i-Pr H CH20CH2CH20CH3 CH3

685 Et Et i-Pr H CH20CH2CH20CH3 CH3

686 n-Pr Et i-Pr H CH20CH2CH20CH3 CH3

687 i-Pr Et i-Pr H CH20CH2CH20CH3 CH3

688 n-Bu Et i-Pr H CH20CH2CH20CH3 CH3

689 i-Bu Et i-Pr H CH20CH2CH20CH3 CH3

690 t-Bu Et i-Pr H CH20CH2CH20CH3 CH3

691 CH2C1 Et i-Pr H CH20CH2CH20CH3 CH3

692 Ph Et i-Pr H CH20CH2CH20CH3 CH3

693 TMS Et i-Pr H CH20CH2CH20CH3 CH3

694 H H CH3 CH3 CH20CH2CH20CH3 CH3

695 CH3 H CH3 CH3 CH20CH2CH20CH3 CH3

696 Et H CH3 CH3 CH20CH2CH20CH3 CH3

697 n-Pr H CH3 CH3 CH20GH2CH20CH3 CH3

698 i-Pr H CH3 CH3 CH20CH2CH20CH3 CH3

699 n-Bu H CH3 CH3 CH20CH2CH20CH3 CH3

700 i-Bu H CH3 CH3 CH20CH2CH20CH3 CH3 Table 2--15

 J o, l R2 R3 R4 R6

701 t "Bu H CH3 CH3 CH20CH2CH20CH3 CH3

702 CH2C1 H .CH3 CH3 CH20CH2CH20CH3 CH3

703 Ph.H CH3 .CH3 CH20CH2CH20CH3 CH3

704 TMS H CH3 CH3 CH20CH2CH20CH3 CH3

705 H CH3 CHS CH3 CH20CH2CH20CH3 CH3

706 CH3 CH3 CH3 CH3 CH20CH2CH20CH3 CH3

707 Et CH3 CH3 CH3 CH20CH2CH20CH3 CH3

708 n-Pr CH3 CH3 CH3 CH20CH2CH20CH3 CH3

709 i-Pr CH3 CH3 CH3 CH20CH2CH20CH3 CH3

710 n-Bu CH3 CH3 CH3 CH20CH2CH20CH3 CH3

711 i-B CH3 CH3 CH3 CH20CH2CH20CH3 CH3

712 t-Bu CH3 CH3 CH3 CH20CH2CH20CH3 CH3

713 CH2C1 CH3 CH3 CH3 CH20CH2CH20GH3 .CH3

714 P CH3 CH3 CH3 CH20CH2CH20CH3 CH3

715 TMS CH3 CH3 CH3 CH20 CH2CH20CH3 CH3

716 H Et CH3 CH3 CH20CH2CH20CH3 CH3

717 CH3 Et CH3 CH3 CH20CH2CH20CH3 CH3

718 Et Et CH3 CH3 CH20CH2CH20CH3 CH3

719 n-Pr Et CH3 CH3 CH20CH2CH20CH3 CH3

720 i-Pr Et CH3 CH3 CH20CH2CH20CH3 CH3

721 n-Bu Et.CH3 CH3 CH20CH2CH20CH3 CH3

722 i-Bu Et CH3 CH3 CH20CH2CH20CH3 CH3

723 t-Bu Et CH3 CH3 CH20CH2CH20CH3 CH3

724 CH2C1 Et CH3 CH3 CH20CH2CH20CH3 CH3 725 Ph Et CH3 CH3 CH20CH2CH20CH3 CH3

726 TMS Et CH3 CH3 CH20CH2CH20CH3 CH3

727 H H Et CH3 CH20CH2CH20GH3 CH3

728 CH3 H Et CH3 CH20CH2CH20CH3 CH3

729 Et H Et CH3 CH20CH2CH20CH3 CH3

730 n-Pr H Et CH3 CH20CH2CH20CH3 CH3

731 i-Pr H Et CH3 CH20CH2CH20CH3 CH3

732 n-Bu H Et CH3 CH20CH2CH20CH3 CH3

733 i-Bu H Et CH3 CH20CH2CH20CH3 .CH3

734 t-Bu H Et CH3 CH20CH2CH20CH3 CH3

735 CH2C1 H Et CH3 CH20CH2CH20CH3 CH3

736 Ph. H Et CH3 CH20CH2CH20CH3 CH3

737 TMS H Et CH3 CH20CH2CH20CH3 CH3

738 H CH3 Et CH3 CH20CH2CH20CH3 CH3

739 CH3 CH3 Et CH3 CH20CH2CH20CH3 CH3

740 Et CH3 Et CH3 CH20CH2CH20CH3 CH3

741 n-Pr CH3 Et CH3 CH20CH2CH20CH3 CH3

742 i-Pr CH3 Et CH3 CH20CH2CH20CH3 CH3

743 n-Bu CH3 Et CH3 CH20CH2CH20CH3 CH3

744 i-Bu CH3 Et CH3 CH20CH2CH20CH3 CH3

745 t-Bu CH3 Et CH3 CH20CH2CH20CH3 CH3

746 CH2C1 CH3 Et CH3 CH20CH2CH20CH3 CH3

747 Ph CH3 Et CH3 CH20CH2CH20CH3 CH3

748 TMS CH3 Et CH3 CH20CH2CH20CH3 CH3

749 H Et Et CH3 CH20CH2CH20CH3 CH3

750 CH3 Et Et CH3 CH20CH2CH20CH3 CH3

Ett ii §OCHC2H:

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 88

 Table 2 1 2 3

 No. Rl R2 R3 R4 R5 R6

1101 H CH3 CH3 CH3 CH20 CH2CH2C1 CH3

1102 CH3 CH3 CH3 CH3 CH20 CH2CH2C1 CH3

1103 Et CH3 CH3 CH3 CH20 CH2CH2C1 CH3

1104 n-Pr CH3 CH3 CH3 CH20CH2CH2C1 CH3

1105 i-Pr CH3 CH3 CH3 CH20CH2CH2C1 CH3

1106 n-Bu CH3 CH3 CH3 CH20CH2CH2C1 CH3

1107 i-Bu CH3 CH3 CH3 CH20CH2CH2C1 CH3

1108 t-Bu CH3 CH3 CH3 CH20CH2CH2C1 CH3

1109 CH2C1 CH3 CH3 CH3 CH20CH2CH2C1 CH3

1110 Ph CH3 CH3 CH3 CH20CH2CH2C1 CH3

1111 TMS CH3 CH3 CH3 CH20 CH2CH2C1 CH3

1112 H Et CH3 CH3 CH20CH2CH2C1 CH3

1113 CH3 Et CH3 CH3 CH20 CH2CH2C1 CH3

1114 Et Et CH3 CH3 CH20CH2CH2C1 CH3

1115 n-Pr Et CH3 CH3 CH20CH2CH2G1 CH3

1116 i-Pr Et CH3 CH3 CH20CH2CH2C1 CH3

1117 n-Bu Et CH3 CH3 CH20CH2CH2C1 CH3

1118 i-Bu Et CH3 CH3 CH20CH2CH2C1 CH3

1119 t-Bu Et CH3 CH3 CH20CH2CH2C1 CH3

1120 CH2C1 Et CH3 CH3 CH20CH2CH2C1 CH3

1121 Ph Et CH3 CH3 CH20CH2CH2C1 CH3

1122 TMS Et CH3 CH3 CH20CH2CH2C1 CH3

1123 H H Et CH3 CH20CH2CH2C1 CH3

1124 CH3 H Et CH3 CH20CH2CH2C1 CH3

1125 Et H Et CH3 CH20CH2CH2G1 CH3

1126 n-Pr H Et CH3 CH20CH2CH2C1 CH3

1127 i-Pr H Et CH3 CH20CH2CH2C1 CH3

1128 n-Bu H Et CH3 CH20CH2CH2C1 CH3

1129 i-Bu H Et CH3 CH20CH2CH2C1 CH3

1130 t-Bu H Et CH3 CH20CH2CH2C1 CH3

1131 CH2C1 H Et CH3 CH20CH2CH2C1 CH3

1132 Ph H Et CH3 CH20CH2CH2C1 CH3

1133 TMS H Et CH3 GH20CH2CH2C1 CH3

1134 H CH3 Et CH3 CH20 CH2 CH2 C1 CH3

1135 CH3 CH3 Et CH3 CH20CH2CH2C1 CH3

1136 Et CH3 Et CH3 CH20 CH2 CH2 C1 CH3

1137 n-Pr CH3 Et CH3 CH20CH2CH2C1 CH3

1138 i-Pr CH3 Et CH3 CH20CH2CH2C1 CH3

1139 n-Bu CH3 Et CH3 CH20 CH2CH2C1 CH3

1140 i-Bu CH3 Et CH3 CH20 CH2CH2C1 CH3

1141 t-Bu CH3 Et CH3 CH20CH2CH2C1 CH3

1142 CH2C1 CH3 Et CH3 CH20CH2CH2C1 CH3

1143 Ph CH3 Et CH3 CH20CH2CH2C1 .CH3

1144 TMS CH3 Et CH3 CH20CH2CH2C1 CH3

1145 H Et Et CH3 CH20CH2CH2C1 CH3

1146 CH3 Et Et CH3 CH20CH2CH2C1 CH3

1147 Et Et Et CH3 CH20CH2CH2C1 CH3

1148 n-Pr Et Et CH3 CH20CH2CH2C1 CH3

1149 i-Pr Et Et CH3 CH20CH2CH2C1 CH3

1150 n-Bu Et Et CH3 CH20CH2CH2C1 CH3 JP01 / 03120

 89 Table 2 1 2 4

 No. Rl R2 R3 R4 R5 R6

1151 i-Bu Et Et CH3 CH20CH2CH2C1 CH3

1152 t-Bu Et Et CH3 CH20CH2CH2C1 CH3

1153 CH2C1 Et Et CH3 CH20CH2CH2C1 CH3

1154 Ph Et Et CH3 CH20CH2CH2C1 CH3

1155 TMS Et Et CH3 CH20CH2CH2C1 CH3

1156 H H i-Pr CH3 CH20CH2CH2C1 CH3

1157 CH3 Hi i-Pr CH3 CH20 CH2GH2C1 CH3

1158 Et H i-Pr CH3 CH20CH2CH2C1 CH3

1159 n-Pr H i-Pr CH3 CH20CH2CH2C1 CH3

1160 i-Pr H i-Pr CH3 CH20CH2CH2C1 CH3

1161 n-Bu Hi-Pr CH3 CH20CH2CH2C1 CH3

1162 i-Bu H i-Pr CH3 CH20CH2CH2C1 CH3

1163 t-Bu Hi-Pr GH3 CH20CH2CH2C1 CH3

1164 CH2C1 Hi i-Pr CH3 CH20CH2CH2C1 CH3

1165 Pli Hi-Pr CH3 CH20CH2CH2C1 CH3

1166 TMS Hi-Pr CH3 CH20CH2CH2C1 CH3

1167 H CH3 i-Pr CH3 CH20CH2CH2C1 CH3

1168 CH3 CH3 i-Pr CH3 CH20CH2CH2C1 CH3

1169 Et CH3 i-Pr CH3 CH20CH2CH2C1 CH3

1170 n-Pr CH3 i-Pr CH3 CH20CH2CH2C1 CH3

1171 i-Pr CH3 i-Pr CH3 CH20CH2CH2C1 CH3

1172 n-Bu CH3 i-Pr CH3 CH20CH2CH2C1 CH3

1173 i-Bu CH3 i-Pr CH3 CH20CH2CH2C1 CH3

1174 t-Bu CH3 i-Pr CH3 CH20CH2CH2C1 CH3

1175 CH2C1 CH3 i-Pr CH3 CH20 CH2CH2C1 CH3

1176 Ph CH3 i-Pr CH3 CH20CH2CH2C1 CH3

1177 TMS CH3 i-Pr CH3 CH20CH2CH2C1 CH3

1178 H Et i-Pr CH3 CH20CH2CH2C1 CH3

1179 CH3 Et i-Pr CH3 CH20CH2CH2C1 CH3

1180 Et Et i-Pr CH3 CH20CH2CH2C1 CH3

1181 n-Pr Et i-Pr CH3 CH20CH2CH2C1 CH3

1182 i-Pr Et i-Pr CH3 CH20CH2CH2C1 CH3

1183 n-Bu Et i-Pr CH3 CH20CH2CH2C1 CH3

1184 i-Bu Et i-Pr CH3 CH20CH2CH2C1 CH3

1185 t-Bu Et i-Pr CH3 CH20CH2CH2C1 CH3

1186 CH2C1 Et i-Pr CH3 CH20CH2CH2C1 CH3

1187 Ph Et i-Pr CH3 CH20CH2CH2C1 CH3

1188 TMS Et i-Pr CH3 CH20CH2CH2C1 CH3 Table 3

Compound Synthesis method Yield ¾-NME data (CDCL) IR data Melting point

 () (° C)

1-001 B 36 2.51 (s, 3H), 2.55 (t, lH), 3.3-3.4 (m, 4H), 2945, 119.1-146.3

 3.78 (s, 3H), 4.05 (s, 3H), 5.32 (d, 2H), 1527,

 7.26 (s, lBD, 7.43 (d, lH), 7.94 (d, lH) .1121,

1-002 B 44 1.83 (t, 3H), 2.52 ( _S) 3H), 3.3-3.4 (m, 4H), 1636,154.9-155.5

3.77 (s, 3H), 4.05 (s, 3H), 5.22 (q _; 2H), 1312,

 7.27 (s, lH), 7.43 (d, lH), 7.94 (d, lH). 1048

 1-012 B 56 1.76 (d, 3H), 2.51 (d, lH), 2.52 (s, 3H), 3.3-1649, 144.6-145.9

 3.4 (m, 4H), 3.79 (s, 3H), 4.05 (s, 3H), 5.7-1507,

6.0 (m, lH), 7.27 (s _; lH), 7.43 (d, lH), 1119,

 7.94 (d, lH).

 1-067 B 27 1.45 (t, 3H), 2.52 (s, 3H), 2.55 (t, 3H), 3.3-2980, 132.1-135.2

 3.4 (m, 4H), 4.05 (s, 3H), 4.14 (q, 2BD, 1515,

5.34 (d, 2H), 7.26 (s, lH) _; 7.44 (d, lH), 1515,

 7.94 (d, lH) .1120,

 1-068 B 33 l, 45 (t, 3H), 1.82 (t, 3H), 2.52 (s, 3H), 3.3-1633, 171.8-172.3

 3.4 (m, 4H), 405 (s, 3H), 413 (q, 2H), 1506,

5.24 (q _; 2H), 7.26 (s, lH), 7.43 (d, lH), 1121,

 7.93 (d, lH). 2 332321321111111111111111111111

1-078 B 21 1.46 (t, 3H), 1.76 (d, 3H), 2.5l (m _; 4H), 3.3-260239506915260693330250540953524 74429230444708224630432471111 2987, 146.9-147.7

 3.4 (m, 4H), 4.05 (s, 3H), 414 (q, 2H), 5.8-096 5666240097800604579774113751 1525,

 6.l (m, l), 7.26 (s, lH), 7.43 (d, lH), 1313,

 7.93 (d, lH).

 1-133 B 98 1.48 (d, 6H), 2.52 (S, 3H), 2.55 (t, lH, 3.3-1649, 172.1-174.0

 3.4 (m, 4H), 4.05 (s, 3H), 4.75 (m, lH), 1492,

5.32 (d, 2H), 7.26 (s, lH) _; 7.44 (d, lH), 1119,

 7.94 (d, lH).

1-134 B 72 1.48 (d, 6H), 1.82 (t, 3H), 2.53 (s, 3H) _; 3.3-1633, 181.2-183.2

 3.4 (m, 4H), 4.05 (s, 3H), 4.75 (m, lH), 1437,

 5.22 (q, 2H), 7.28 (s, lH), 7.44 (d, lH), 1048

 7.93 (d, lH).

 1-135 B 87 1.24 (t, 3H), 1.48 (d, 6H), 2.0-2.4 (m, 2H), 2977; 1632, 168.8-169.5

 2.53 (s, 3H), 3.3-3.4 (m, 4H), 4,05 (s, 3H), 1525, 1494,

 475 (m, lH), 5.25 (t, 2H), 7.27 (s, lH), 1435, 1311,

 7.44 (d, lH), 7.93 (d, lH) .1052

 1-136 B 40 0.91 (t, 3H), 1.3-1.6 (m, 2H), 1.48 (d, 6H), 2979, 1634, 101.0-104.8

2.0-2.2 (m, 2H) ₎ 2.53 (s, 3H), 3.3-1524, 1432,

 3.4 (m, 4H), 4.05 (s, 3H), 475 (m, lH), 1312,1049

 5.27 (t, 2H), 7.26 (s, lH), 7.43 (d, lH),

 7.93 (d, lH).

 1-142 B 81 1.48 (d, 6H), 2.53 (s, 3H), 3.3-3.4 (m, 4H), 2984, 1642, 139.0-141.6

 4.04 (s, 3H), 4.75 (m, lH), 5.53 (s, 2H), 1526, 1434,

 7.30 (s, lH), 7.33 (s, 5H), 7.44 (d, lH), 1314, 1202,

 7.9l (d, lH). 1046

 1-143 B 98 0.13 (s, 9H), 1.49 (d, 6H), 2.53 (s, 3H), 3.3-3007, 1638,

 3.4 (m, 4H), 4.05 (s, 3H), 4.75 (m, lH), 1529, 1498,

 5.30 (s, 2H), 7.27 (s, lH), 7.44 (d, lH), 1433, 1310,

7.94 (d, lH) ._ 1043 Table 3-2

Compound Synthesis method 1H-NMR data (CDCL) IR data Melting point

 (° C)

1-144 B 65 1.52 (d, 6H), 1.77 (d, 3H), 2.49 (d, lH), 2978, 1646, 155.9-156.6

 2.52 (s, 3H), 3.3-3.4 (m, 4H), 4.05 (s, 3H), 1523, 1491,

 Y 4.76 (m, ll¾, 5.7-6.0 (m, ffl), 7.27 (s, lH), 1315, 1047

 rate

 7.43 (d, lH), 7.93 (d, lH).

 1-155 B 86 1.20 (t, 3H), 1.5l (d, 6ED, 2.05 (m, 2H), 3266, 2973, 151.4-151.9

2.49 (d, lH), 2.53 (s _; 3H), 3.3-3.4 (m, 4H), 1650, 1527,

 4.05 (s, 3H), 475 (m, lH), 5.7_5.9 (m, lH), 1489, 1423,

 7.27 (s, lH), 7.44 (d, lH), 7.93 (d, lH) .1316, 1203,

 1049

 V-265 A 1.45 (t, 3H), 1.53 (s, 6H), 2.2-2.4 (m, 2H), 1646, 1522,

 2.46 (s, 3H), 2.54 (t, lH), 2.78 (s, 3H), 1508,1280,

 3.3-3.5 (m, 2H), 4.13 (q, 2H), 5.32 (d, 2H), 1124

 7.05 (s, lH), 7.23 (s, lH).

 V-266 B 70 1.45 (t, 3H), 1.53 (s, 6H), 1.83 (t, 3H), 2.3-2930 1648, 171.1-171.9

 2.5 (m, 2H), 2.46 (s, 3H), 2.78 (s, 3H), 1527 1508,

 3.3-3.5 (m, 2H), 4.12 (q, 2H), 5.23 (q, 2H), 1279 1129

 7.05 (s, lH), 7.24 (s, lH).

 V-276 B 61 1.46 (t, 3H), 1.54 (s, 6H), 1.76 (d, 3H), 2.3-2953 1643, 154.9-155.5

2.5 (m, 2H) _; 2.46 (s, 3H), 2.49 (d, lH), 1530 1513,

2.78 (s, 3H), 3.3-3.5 (m, 2H), 4.13 (q, 2H) ₃ 1287 1128

 5.7-6.Odn.lH), 7.04 (s, lH), 7.24 (s, lH).

 VII-067 B 39 1.46 (t, 3H), 2.3l (s, 3H), 2.55 (t, lH), 3.2-3244, 2996, 165.8-254.6

 3.6 (m, 4H), 4.14 (q, 2H), 5.32 (d, 2H), 1650 11 1 11111111111112 66664555651511133,

7.27 (s, lH) _; 7.47 (d _; lH), 7.67 (d, lH) .1508 1388849300400280 43444690 4994944053,

 1201 1118

 VII-068 B 40 1.45 (t, 3H), 1.82 (t, 3H), 2.3l (s, 3H), 3.2-2994, 1647, 152.0-155.8

 3.6 (m, 4H), 4.13 (q, 2H), 5.22 (q, 2H), 1526 1507,

 7.27 (s, lH), 7.47 (d, lH), 7.67 (d, lH) .1230 1121

VII-793 B 18 2.56 (t, lH), 3.4-3.7 (m, 4H), 3.79 (s, 3H), 3291 1639,

 5.29 (d, lH), 7.28 (s, lH), 7.51 (d, lH), 1538 1514,

 7.75 (d, lH) .1294.1203,

 1135

VII-794 B 20 1.83 (t, 3H), 3.4-3.7 (m, 4H), 3.77 (s, 3H), 2964 _;

 5.20 (q, lH), 7.26 (s, lH), 7.5l (d, lH), 1536

 7.75 (d, lH). 1292

VII-859 B 23 1.46 (t, 3H), 2.56 (t, lH), 3.4-3.7 (m, 4H), 3283 158.3-159.6

4.14 (q _; 2H), 5.32 (d, lH), 7.29 (s _; lH), 1532

 7.52 (d, lH), 7.75 (d, lH) .1293

VII-860 B 29 1.46 (t, .3H), 1.85 (t, 3H), 3.4-3.6 (m, 4H), 2997 140.1-141.8

 4.15 (q, 2H), 5.23 (q, lH), 7.28 (s, lH), 1533

 7.5l (d, lH), 7.75 (d, lH). 1294

VII-870 B 14 1.46 (t, 3H), 1.77 (d, 3H), 2.52 (d, lH), 3.4-3272 149.5-150.4

 3.6 (m, 4H), 4.15 (q, 2H), 5.7-6.0 (m, lH), 1528

 7.28 (s, lH), 7.5l (d, lH), 7.75 (d, ffl) .1311

VII-826 B 14 1.97 (s, 3H), 2.56 (t, lH), 3.3'3.7 (m, H), 2985 169.8-170.2

3.76 (s, 3H) _; 4.83 (d, 2H), 7.47 (d, lH), 1518

 7.75 (d, lH) .1303

1119

 (0.) (%)

Πθαθ) ΗΗΝ-Η _Τ

 ε—mine ε 绻

Ζ6

0∑IC0 / T0df / X3d 66Ϊ6 ./Ϊ0 O Table 3-4

 Compound Synthesis method Yield Ή-NM data (CDCL) IR data Melting point (%) (° C)

IX- 134 B 58 1.48 (d, 6H), 1.68 (s, 6H), 1.82 (t, 3H), 2990, 1636, 171.2-172.0

 2.45 (s, 3H), 3.38 (s, 2H), 4.76 (hept, lH), 1531,1436,

5.20 (q, 2H), 7.27 (s, lH) _; 7.42 (d, lH), 1298, 1123

 7.64 (d, lH).

 IX-100 B 92 1.43 (t, 3H), 1.68 (s, 6H), 1.83 (s'3H), 3240, 2989,

 2.44 (s, 3H), 2.56 (t, lH), 3.37 (s, 2H), 1746,

 4.05 (q, 2H), 489 (d, 2H), 7.35 (d, lH), 1530, 1230,

 7.64 (d, lH) .1066

 IX-397 B 39 1.15 (t, 3H), 1.70 (s, 6H), 2.55 (t, lH), 3249,1650,167.1-168.4

 2.95 (q, 2H), 3.38 (s, 2H), 3.78 (s, 3H), 1534, 1518,

 5.29 (d, 2H), 7.25 (s, lH), 7.40 (d, lH), 1304, 1129

 7.63 (d, lH).

 XI-793 A 39 1.30 (t, 3H), 1.47 (fc, 3H), 2.55 (t, lH), 3.6-2983, 1652,

 3.9 (m, 4H), 4.15 (q, 2H), 5.3 l (t, lH), 1533, 1508,

 5.32 (d, 2H), 7.30 (s, lH), 7.60 (d, lH), 1313, 1198

 7.77 (d, lH).

ΧΠ-001 A 59 1.69 (s, 6H), 2.55 (t, lH), 3.20 (s _; 3H), 2923, 1650, 172.8-173.9

 3.37 (s, 2H), 4.64 (s, 2H), 5.22 (d, 2H), 1539, 1306,

 7.34fe, lH), 7.44 (d, lH), 7.73 (d, m).

XII-397 A 63 1.70 (s, 6H), 2.56 (t, lH), 3.23 (s _; 3H), 3.2-2914, 1651, 134.2-136.6

 3.6 (m, 4H), 3.37 (s, 2H), 3.79 (s, 3H), 1541, 1294,

 4.77 (s, 2H), 5.20 (d, 2H), 7.37 (s, lH), 1123

 7.45 (d, lH), 7.73 (d, lH).

 XII-793 A 75 1.7l (s, 6H), 2.64 (t, lH), 3.39 (s, 2H), 3.4-2962, 1645,

 3.7 (m, 4H), 3.78 (s, 3H), 4.78 (s, 2H), 1535, 1519,

 5.19 (d, 2H), 7.37 (s, lH), 7.47 (d, lH), 1301, 1125

 7.74 (d, lH).

Production Example 2

Table 1 shows ¹ H-NMR and IR spectra of other compounds of the present invention produced in the same manner as in Production Example 1. Table 4

 Compound Synthetic method Yield-hire R data (CDCL) IR data Melting point

 (%) (.C)

VII-529 A 48 1.15 (t, 3H), 1.48 (d, 6H), 2.55 (t, lH), 3261, 2361,

 2.73 (q, 2H), 3.3'3.6 (m, 4H), 4.5-1640, 1530,

 4.9 (m, lH), 5.30 (d, 2H, 7.26 (s, lH), 1497, 1432,

 7.45 (d, lH), 7.66 (d, lH) .1309, 1128

 YIII-529 A 54 1.15 (t, 3H), 1.48 (d, 6H), 1.56 (d, 3H), 2359, 1641,

 2.60 (t, lH), 2.82 (q, 2H), 3.2-4.0 (m, 3H), 1527, 1496,

 4.5-5.0 (m, lH, 5.30 (d, 2H), 7.29 (s, lH), 1305, 1125

 7.46 (d, lH), 7.64 (d, lH).

VIII-1123 A 56 1.48 (d, 6H), 1.56 (d _; 3H), 2.56 (t, lH), 3266, 2981, 157.1-158.0

 2.64 (s, 3H), 3.2-3.9 (m, 3H), 4.5-2359, 1729,

 5.0 (m, lH), 5.29 (d, 2H), 7.24 (s, lH), 1646, 1531,

7.3l (s, lH). 1299, 1136 IX-529 A 29 1.16 (t, 3H), 1.48 (d, 6H), 1.7l (s, 6H), 3253, 2982,

 2.55 (t, lH), 2.96 (q, 2H), 3.38 (s, 2H), 4.5-2364, 1737,

 5.0 (m, lH), 5.31 (d, 2H), 7.25 (s, lH), 1640, 1527,

 7.41 (d, lH), 7.63 (d, lH) .1304, 1128

 XI-859 A 39 1.29 (t, 3H), 1.46 (t, 3H), 2.57 (t, lH), 3.6-3273, 2983,

 3.9 (m, 3H3, 4.15 (q, 2H), 5.3l (d, 2H), 1652, 1533,

 7.30 (s, lH), 7.61 (d, lH), 7.76 (d, lH) .1508, 1313,

 1198, 1160,

 1133 Manufacturing Example 3

Formula Other compounds of the present invention prepared by Method A in Preparation Example 1, the structural formula of the starting compound, and the reaction yield in Table 5, also, ¹ H- NMR, and IR spectra sixth It is shown in the table. Table 5

Table 6

 Compound 11 data (CDCL) IR data

XIV-001 1.4l (t, 3H), 2.53 (t, lH), 3.36 (m, 2H), 3.50 (m, 2H),

 3.77 (s, 3H), 08 (m, 2H), 5.25 (d, 2H), 7.34 (s, lH),

 7.44 (m, 2H).

 XIV-002 1.43 (s, 3H), 1.45 (s, 3H), 2.26 (m, lH), 2.54 (m, lH), 139-141

 3.5l (m, 4H), 4.62 (d, 2H), 4.68 (m, lH), 5.24 (d, 2H),

 7.35 (s, lH), 7.5l (m, 2H).

XIV-003 1.44 (s, 3H), 1.46 (s, 3H), 2.44 (m, 1H), 3.19 (m, 2H) _;

 3.42 (m, 2H), 471 (m, lH), 4.93 (s, 2H), 5.24 (d, 2H),

 7.18-7.5l (m, 8H).

XIV-004 1.45 (t, 3H), 2.1-2.4 (m, 2H), 2.31 (s, 3H), 2.56 (t, lH), 2958, 1645, 1529,

 2.63 (s, 3H), 3.3-4.l (m, 5H), 4.14 (q, 2H), 5.3l (d, 2H), 1509, 1297, 1121

7.2l (s, lH).

 XIV-005 1.48 (d, 6H), 1.49 (s, 6H), 2.43 (s, 3H), 2.55 (t, lH), 3276, 2933, 1699,

 3.49 (s, 2H), 45-5.0 (m, lH), 5.31 (d, 2H), 7.26 (s, lH), 1647, 1530, 1319, 7.6l (d, lH), 7.89 (d, lH) . 1191, 1129

 XIV-006 1.24 (d, 6H), 1.48 (d, 6H), 2.56 (t, lH), 2.76 (s, 3H), 3279, 2977, 2933,

2.5-4.3 (m, 5H) ₎ 3.7-4.2 (m, lH), 4.5-5.0 (m, lH), 1652, 1532, 1306, 5.29 (d, 2H), 7.26 (s, lH), 7.63 (s , lH) .1128, 1052

 XIV-007 1.48 (t, 3H), 2.58 (t, lH), 3.67 (s, 4H), 4.17 (q, 2H), 3270, 2962, 2226,

5.30 (d, 2H), 7.42 (s, lH), 7.8l (d, lH) _; 8.04 (d, lH). 1652, 1527, 1508,

 1303, 1186, 1119

 XIV-008 1.32 (d, 6H), 1.45 (t, 3H), 1.72 (s, 6H), 2.52 (t, lH 3267, 2966, 1650,

 3.33 (s, 2H), 3.3-3.7 (m, lH), 4.14 (q, 2H), 5.28 (d, 2H), 1535, 1519, 1306, 7.5l (s, lH), 7.6l (s, 2H ) .1137

 XIV-009 1.46 (t, 3H), 2.56 (t, lH), 3.53 (s, 3H), 3.69-3278, 2943, 1650,

 3.75 (m, 2H), 4.14 (q, 2H), 5.30 (d, 2H), 5.3'5.5 (m, lH) 1532, 1306, 1149, 7.21 (s, lH), 7.65 (d, lH), 8.02 (d, lH). 1139

 XIV-010 1.65 (s, 9H 2.59 (t, lH), 3.43 (m, 2H), 3.59 (t, 2H), 154

 5.32 (s, 2H), 7.10 (s, lH), 7.50 (d, lH), 7.72 (d, lH).

XIV-011 1.46 (t, 3H), 1.55 (s, 6H), 2.59 (t, lH), 3.48 (s, 2H), 3261, 1641, 1532,

 4.14 (q, 2H), 5.3l (d, 2H), 7.28 (s, lH), 7.32 (s, lH) .1503, 1312, 1196,

 1140

 XIV-012 1.47 (t, 3H), 1.54 (s, 6H), 2.40 (s, 3H), 2.57 (t, lH 3268, 2974, 1646,

 3.39 (s, 2H), 415 (q, 2H), 5.3l (d, 2H), 7.28 (s, lH), 1531,1507,1303, 7.38 (s, lH), 7.59 (s, lH). , 1132, 860,

732

Examples of herbicides

 (1) Preparation of herbicide

 Talc (trade name: Ziglite, manufactured by Ziglite Industry Co., Ltd.) 97 parts by weight, alkylaryl sulfonate as a surfactant (trade name: Neoperex, manufactured by Kao Atlas Co., Ltd.) 1.5 Parts by weight and 1.5 parts by weight of Noun and anion type surfactants (Solpol 80 OA, manufactured by Toho Chemical Industry Co., Ltd.) were uniformly ground and mixed to obtain a carrier for a wettable powder.

 90 parts by weight of this carrier for wettable powders and 10 parts by weight of the compound of the present invention were uniformly ground and mixed to obtain herbicides. As a herbicide comparative example, the following compounds (A), (B) and (C) were used and prepared in the same manner.

Compounds (A) and (B): compounds described in WO 95/04054

Compound (C) Compound described in WO 96/25412

Compound (A)

Compound (B)

Compound (C)

( 2 ) 除草効果、 作物薬害の判定基準

(2) Criteria for herbicidal effect and crop damage

 The criteria for herbicidal efficacy and crop damage are:

 Residue weight no treatment ratio-(Residue weight of treated area / residual weight of untreated area) X 100

And applied in the following biological tests. Herbicidal effect No residue ratio

 0 8 1 ~; L 0 0

 1 6 1 ~ 8 0

 2 4 1 to 6 0

 3 2 1 ~ 4 0

 4 1 ~ 2 0

 5 0

 Crop damage

 1 0 0

 Sat 9 5-9 9

 + .90 ~ 94

 +++ 80-89

 0-7 9

 (3) Biological test (field soil treatment test)

Weed seeds of ichibi, ragweed, chickweed, shiroza, agoitou, mehisiba, enokorogosa and sow seeds of 1/500 arenal pegner pot filled with field soil are seeded, and after covering with soil as described in (1) above. A predetermined amount of the herbicide thus obtained was suspended in water, and sprayed uniformly on the soil surface with a liquid amount equivalent to 2000 liters of hectare. Thereafter, the plants were grown in a greenhouse, and on the 20th day after the treatment, the herbicidal effect and phytotoxicity to corn were determined according to the criteria of (2). Table 7 shows the results. Table 7-1

(Soil treatment test)

ga.i. = g active ingredient Table 7-2

 (Soil treatment test)

第 7表の結果から、 本発明の除草剤は、 トウモロコシに薬害を及ぼさず、 且つ 単子葉から双子葉までの広範な重要畑地雑草を低薬量で選択的に防除できること が確認された。 これに対して化合物 （A ( B ) 及び （C ) は、 明らかに除草効 果が劣ることがわかる。

From the results in Table 7, it was confirmed that the herbicide of the present invention did not cause phytotoxicity to corn and that it could selectively control a wide range of important upland weeds from monocots to dicots at a low dose. On the other hand, it can be seen that the compounds (A (B) and (C)) have clearly poor herbicidal effects.

 (4) Biological test (field foliage treatment test)

Weed seeds of Ichibi, Ragweedweed, Hakobe, Shiroza, Agogeto, Mehisipa, Enokorogusa and soybean seeds in a 1Z500 al arenel pot filled with field soil are grown and grown in a greenhouse after covering the soil. At the 34th leaf stage of these plants, a predetermined amount of the herbicide obtained in the above (1) was suspended in water, and sprayed uniformly onto the foliage at a liquid equivalent to 2000 liters / hectare. After that, it is grown in a greenhouse and after treatment 30 On the day, the herbicidal effect and phytotoxicity to corn were determined according to the criteria of (2). Table 8 shows the results. Table 8-1

 (Foliage treatment test)

 Weeding effect

 ヽ ヽ ヽ ヽ π ノ

 Compound 1 Compound 1 ゥ

 Hikusaken Como

No. ga.i./ha Sino

 Blog

 Kashi

 T-i 5 5 5 5 5 5 4

 5 5 5 5 4 5 3

 1-2 100 5 5 5 5 5 5 5

 30 5 5 5 5 5 4 5

1-12 100 5 5 5 5 5 5 5

 30 5 5 5 5 4 4 4

1-67 100 5 5 5 5 5 5 5

 30 5 5 5 5 5 5 5

1-68 100 5 5 5 5 5 5 5

 30 5 5 5 5 4 4 4

1-78 100 5 5 5 5 5 5 5

 30 4 5 5 5 4 4 3

V-265 100 5 5 5 5 5 5 4

 30 5 4 4 5 5 5 3

V-266 100 4 5 5 5 4 5 4

 30 3 4 4 5 3 4 3

V-276 100 4 5 5 5 4 5 4

 30 4 5 4 5 4 4 3

VII-67 100 5 5 4 5 5 5 4

 30 5 5 3 4 4 4 3

VII-68 100 5 5 5 5 5 5 4

 30 5 4 5 5 4 3 3

VII-793 100 5 5 5 5 5 4 4

30 4 4 4 5 5 3 3 Table 8-2 Herbicidal effect 3 宝 s treasure

サソ ィ 1 ノ 口 卜 グ コ ゥ サ シ 1 mouth W

Sssssssssssssssssssss

V 丄 丄 / y Upper UU 0 0 0 0 0 4 4

 oU 0 0 4 ο 4 4 0 Q

 1UU 0 0 5 0 0 4

 4 4 4 0 er 4 4 4 Q

 O

丄 丄 luu 5 Ο 5 5 5 5

 5 0 4 0 0 0 4

 IX "2 100 5 5 5 0 0 O 4

 30 4 5 0 5 0 0 o o o

丄 X-3 100 5 0 5 5 0 Ο 4

 ol) 0 0 4 0 4 4 O

 1UU 5 ο κ 0 0 t? 0 4

 o

 U o o

 D 4 4 4 o Import 丄 U 1UU 0 0 O 0 0 ο O

 oU 0 0 0 0 0 Q Q

 ΰ O

 TV c 丄-1 丄 1 丄 JLUU er

 O 0 0 0 o Ο O oU A κ κ ϋ

丄 τγ-topι ^ top 5 5 5 5 5 5 5

 30 4 5 5 5 5 5 4

 ΙΧ-67 100 5 5 4 5 5 5 4

 30 5 5 3 5 4 4 3

 ΙΧ-68 100 5 5 4 5 5 5 5 Sat

 30 5 5 3 5 5 4 3

 IX-133 100 5 5 5 5 5 5 5

30 5 5 5 5 5 4 4 Table 8-3

 (Foliage treatment test)

第 8表の結果から、 本発明の除草剤は、 トウモロコシに薬害を及ぼさず、 且つ 単子葉から双子葉までの広範な重要畑地雑草を極めて低薬量で選択的に防除でき ることが確認された。 これに対して化合物 ) (B ) 及び （C ) は、 除草効果 が劣ることがわかる。

From the results in Table 8, it was confirmed that the herbicide of the present invention does not cause harm to corn and can selectively control a wide range of important upland weeds from monocots to dicots at extremely low dose. Was. On the other hand, it can be seen that the compounds) (B) and (C) have poor herbicidal effects.

(5) Biological test (field foliage treatment test 2)

Weed seeds, corn and wheat, of ichibi, ragweed, chickweed, shiroza, crabgrass, enokorogosa are sowed in a 1 500 000 arel Wagner pot filled with field soil, and after covering the soil, in a greenhouse. At the 3-4 leaf stage of these plants, a predetermined amount of the herbicide obtained in the above (1) was suspended in water, and sprayed uniformly onto the foliage at a liquid volume of 2000 liters / hectare. . Thereafter, the plants were grown in a greenhouse and treated at 30 B to determine the herbicidal effect and phytotoxicity to corn and wheat according to the criteria of (2). Table 9 shows the results. Table 9-1 1

 (Foliage treatment test 2)

Herbicidal effect ¾5 鱼 ブ ヽ コ コ コ 化合物 化合物_{¾ ¾ ¾ ¾}コ ノ

No. ga.i./ha Sano ^

 G

 Sashimi

1-133 100 5 5 3 5 5 5 One soil

 30 5 3 2 5 5 5 1

1-134 100 4 4 3 5 5 5 + Sat

 30 3 2 2 4 5 4

1-135 100 5 5 3 5 5 5

 30 4 2 2 5 5 4 ―

1-142 100 5 5 4 5 5 5 Sat + +

 30 5 5 2 5 5 5 1 +

1-143 100 5 4 5 5 5 5 ― +

 30 4 3 3 4 5 5 ― Sat

1-144 100 4 4 4 5 5 5 ― Sat

 30 3 2 2 3 5 5 1 1

V-232 100 5 5 5 5 5 4 ― ―

 30 5 3 3 5 5 3 ― One

V-233 100 5 5 5 5 5 4 ― One

 30 4 3 4 5 3 2 ― ―

V-243 100 5 5 5 5 4 4 ―

 30 4 5 4 5 2 2 ― ―.

VII-1 100 5 5 4 5 5 4

 30 5 5 3 5 3 3

 VII-529 100 5 4 5 5 5 4

 30 5 3 5 5 5 2

 VII-859 100 5 4 5 5 4 3

 30 5 2 3 5 3 2

 VII-860 100 5 4 5 5 4 3

30 4 3 3 4 3 2 Table 9-2

(Foliage treatment test 2)

Note η.α. = not detected 0

 106 Table 9 1 3

 (Foliage treatment test 2)

第 9表の結果から、 本発明除草剤は、 トウモロコシもしくはコムギに薬害を及 ぼさず、 且つ単子葉から双子葉までの広範な重要畑地雑草を極めて低薬量で選択 的に防除できることが確認された。 これに対して化合物 （Α；)、 (Β ) および（C ) は、 除草効果およびコムギに対する選択性が劣ることがわかる。 産業上の利用の可能性

From the results in Table 9, it was confirmed that the herbicide of the present invention does not cause harm to corn or wheat and can selectively control a wide range of important upland weeds from monocots to dicots at extremely low dose. Was done. On the other hand, it can be seen that the compounds (Α;), (Β) and (C) have poor herbicidal effects and poor selectivity for wheat. Industrial applicability

The acetylene derivative of the present invention can be used for tow in both soil treatment and foliage treatment. It does not cause phytotoxicity to field crops such as sorghum and can selectively control a wide range of field weeds such as grasses and broadleaf weeds at low doses.

Claims

Scope of claim General formula (I)

 (Expression

(However, when X represents an asymmetric group, the bond on the left is bonded to the benzene ring, and the bond on the right is bonded to the Y moiety.) Represents a group represented by Y is the formula

 (However, when Υ represents a left-right asymmetric group, the bond on the left is bonded to the X part, and the bond on the right is bonded to the ζ part.) Represents a group represented by  ζ is oxygen ― S-

R 40 R ⁴⁰ X ⁷  ~ N— S one ■ N— C one 0 ₂  (However, when Z represents an asymmetric group, the bond on the left is bonded to the benzene ring, and the bond on the right is bonded to the Y moiety.) Represents a group represented by  However, the following general formula (V):

When the substituent represented by is bonded to the benzene ring at the meta position to R ⁵ , Z is not —S ー₂ —. Y is the expression Y is the expression r ₃₀  • ~ N— When X is a group represented by the formula: R ²⁶ —— C = N—— It cannot be a group represented by. Y is the expression

Ζ is a group represented by the formula  ― 0― S-one ― S-one 0 0 is not a ₂ 0 ₂ in a group represented by.  When Υ represents an oxygen atom, X is R ⁷ R ²⁶ R ²⁷  —— represents a group represented by c— or c = c—, and z is a group represented by the formula X ⁷ R ³⁵  II I  —— C—— —— C—— or —— S- It represents a group represented by 36 _Or .  When Y represents a sulfur atom, is represented by the formula ——

Wherein z is a group represented by the formula

Represents a group represented by  Y is the formula S

X is an oxygen atom or a group represented by the formula  ° 0 ゝ "OR 10

And Z represents a group represented by the formula

Represents a group represented by R ¹ is a hydrogen atom, a halogen atom, one or two oxygen atoms and Z or a sulfur atom may be interrupted by, also have good C Cs-chain alkyl group or a C ₃ be ~ a halogen atom C ₆ cyclic alkyl group or a C ₂ - C ₆ alkenyl, - le group, C ₂ to c ₆ haloalkenyl group, c ₂ to c ₆ alkynyl group, Shiano group, a carboxyl group, (Ji-Ji alkoxy) Karuponiru group, tri (CiC alkyl) silyl group, C ₁ -C ₆ alkylthio group, C i Ce alkylsulfiel group, C ₁ -C ₆ alkyl sulfonyl group, substituted or unsubstituted phenylthio group, substituted or unsubstituted phenyl Sulfinyl group, substituted or unsubstituted phenylsulfonyl group, Ci ^ Ce Represents an alkoxy group, a substituted or unsubstituted phenoxy group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted 5- or 6-membered aromatic heterocyclic group. It may be partially or completely oxidized. R ² is a hydrogen atom, a halogen atom, one or two oxygen atoms and / or sulfur atom may be interrupted, and also good C Ce-chain alkyl group or a C ₃ ~ have a halogen atom C ₆ cyclic alkyl group or a C ₂ -C ₆ alkenyl group,, C ₂ to c ₆ Haroanorekeniru group, C ₂ -C ₆ Arukieru group, Shiano group, a carboxyl group, (CiC alkoxy) carbonyl group, tri (CiC alkyl) silyl group, substituted or unsubstituted phenyl group, or substituted or unsubstituted 5- or 6-membered aromatic heterocyclic group. The sulfur atom may be partially or completely oxidized by oxygen. R ³ may be interrupted by a hydrogen atom, one or two oxygen atoms and / or sulfur atoms, and may have a halogen atom.C _{1 to} C ₆ chain alkyl group or C ₃ -C ₆ cyclic alkyl group or a C ₂ -C ₆ Arukeeru group,, C ₂ -C ₆ Haroa alkenyl group, a C ₂ -C ₆ alkynyl group, the sulfur atom is optionally partially or fully oxidized by oxygen Is also good. R ⁴ is a hydrogen atom, one or two oxygen atoms and Z or a sulfur atom may be interrupted by, also good Ci～C ₆ chain alkyl group which may have a halogen atom or c ₂ ~, c ₆ alkenyl group, c ₂ to c ₆ Haroarukeeru group, c _{2-c 6} alkynyl group, a Shiano group, a carboxyl group or a (Ji-Ji alkoxy) carbonylation group, the sulfur atom is partially or by oxygen It may be completely oxidized. R ⁵ may be interrupted by a hydrogen atom, a halogen atom, a nitro group, one or two oxygen atoms and / or a sulfur atom, and may have a halogen atom A C ₆ -C ₆ chain alkyl group or a C ₃ -C ₆ cyclic alkyl group, or a carboxyl group, a cyano group, a thiocyano group, a C ₁ -C ₄ alkoxyl group; ₁ ～〇 ₄ haloalkoxyl group, (Ci C alkoxy) Karuponiru group, a mercapto group, alkylthio O group, Ci C alkylsulfide El group, C ₁ -C ₄ alkylsulfonyl group, c ₂ to c ₆ alkenyl - le group, c ₂ to c, Roaruke - group, or c ₂ shows a to c _s alkynyl group, the C Ce-chain alkyl group or a C ₃ -C ₆ sulfur atoms in the cyclic alkyl group'm connexion partial or complete oxygen It may be oxidized. R ⁶ may be interrupted by a halogen atom, a -toro group, one or two oxygen atoms and / or sulfur atoms, and may have a halogen atom.CiC ₆ chain alkyl group or C _{6 3 to} C ₆ cyclic alkyl group, or carboxyl group, cyano group, thiocyano group, C ₁ -C ₄ alkoxyl group, C ₁ -C, loalkoxyl group, (〇-C ₄ alkoxy) carboel group, mercapto group, Ci C alkylthio group, -C ₄ Arukirusu / Refiniru group, a C i~C ₄ alkylsulfonyl El group, C ₂ -C ₆ an alkenyl group, c ₂ to c ₆ Haroarukeeru group, or c ₂ to c ₆ alkynyl group, the c ~. _The sulfur atom contained in the _6- chain alkyl group or the c ₃ -c ₆ cyclic alkyl group may be partially or completely oxidized by oxygen. Nos. 1 to ⁷ each represent an oxygen atom or a sulfur atom. R ⁷ and R ⁸ may be each independently interrupted by a hydrogen atom, a halogen atom, a nitro group, one or two oxygen atoms and / or sulfur atoms, and have a halogen atom. A C i -C ₆ chain alkyl group or a C ₃ -C ₆ cyclic alkyl group, or a carbonyl group, a cyano group, a Ci C alkoxyl group, a Ci C haloalkoxy nole group, a (C i C alkoxy) carbonyl group , C CA alkyl Chiomoto, Ci C alkylsulfide - le group, Ci C alkylsulfonyl El group, the formula _{^{-CHR 37 N0 2, -CHR 37 NR}} 13 R 14, - CHR 37 P (= θ) (OR 38) _2, -NR ¹³ R ^14, one NR ³⁷ COR ^39, one NR ³⁷ C0 ₂ R ^38, one NR ³⁷ S0 ₂ R ^39, one _{^{OCOR 39, - OCO 2 R 37}} , -OCONR 13 R 14, -OCHR 37 CN , One O CHR ³⁷ COR ³⁹ , -OCHR ³⁷ C0 ₂ R ³⁸ ,-OC HR ³⁷ C ON R ¹³ R ¹⁴ , — S0 ₂ NR ¹³ R ¹⁴ , one OS0 ₂ R ³⁹ , -0-N = CR ¹³ R ³⁷ , —P (= 0) (OR ³⁸ ) ₂ , one OP (= 0) (OR ³⁸ ) _2, a group represented by a substituted or unsubstituted phenylene group, or a substituted or unsubstituted 5-membered or 6-membered ring aromatic heterocyclic group indicates, the _6-chain alkyl group or a C ₃ -C ₆ sulfur atom in the cyclic alkyl group may be by connexion partially or completely oxidized to oxygen. R ⁹ represents a hydrogen atom, a Ci Cs alkyl group, a C Cs haloalkyl group, one COR ³⁹ or one SO ₂ R ³⁹ . R ^{1 Q} may be interrupted by a hydrogen atom, one or two oxygen atoms and / or a sulfur atom, and may have a halogen atom. Ci to C ₆ chain alkyl group or C ₃ -C ₆ cyclic alkyl group or a C ₂ -C _B alkenyl,, C ₂ ~C ₆ Haroa Rukeeru group, C ₂ -C ₆ alkynyl group, or the formula ^{-COR 3 -CO, R 37 CH R} 37 CN, -CHR 37 COR 39, - C HR 37 CO 2 R 38, -CHR ^ CONR 1 3 R 14, -CONR ¹³ R ¹⁴ , a group represented by S 0 ₂ R ³⁹ , wherein the sulfur atom contained in the C Cs chain alkyl group or the C ₃ to C ₆ cyclic alkyl group is partially or completely oxidized by oxygen. May be. R ¹¹ and R ¹² are each independently a hydrogen atom, a nitro group, a carboxyl group, shea Anomoto, CC alkyl group, Ci C haloalkyl group, (Ci~C ₄ alkoxy) carbo - the group or one COR ³⁹ Show. R ¹³ is a hydrogen atom, C ₁ -C ₆ alkyl group, Ci C ₄ haloalkyl group or a substituted young properly unsubstituted Hue - show Le group. R ¹⁴ represents a hydrogen atom, a halogen atom, a CiC alkyl group or a 〇-〇, mouth alkyl group. R ^{15 to} R ²³ , R ²⁶ and R ²⁷ each represent a hydrogen atom, a halogen atom, Represents an alkyl group or an alkyl group having ₁ to ₄ amino acids. R ²⁴ and R ²⁵ are each a hydrogen atom, a halogen atom, 〇 to. Alkyl group, C ₁ -C ₄ haloalkyl group, alkoxyl group, ◦ ~. , Mouth alkoxy group, a carboxyl group, (. ~ Alkoxy) carboxamide group, alkyl thio group, C i~C ₄ alkylsulfide El group, C i~C ₄ alkylsulfonyl group, an amino group, a mono (Ci C alkyl ) Represents an amino group or a di (CiC alkyl) amino group. R ^28, 1 ²⁹及Pi 1 ^{31-1 34} are each a hydrogen atom, a halogen atom, a C ₁ -C ₄ alkyl or C ~ C ₄ C port alkyl group. R ³⁵ and R ³⁶ are each independently a hydrogen atom, a halogen atom, an alkyl group, ～〇, mouth alkyl, Ci C force indicating an alkoxyl group, or R 3 ^5, R ³⁶ and connexion such together the carbon atoms to which they are attached, wherein

May be formed. R ³⁰ , R ³⁷ , ¹³⁸ and 14 ⁽³ each represent a hydrogen atom or a thio-alkyl group. 1 ³⁹ 〇 ₁ ～〇 ₄ Arukiru group, Ji-Ji, showing the mouth alkyl group or a substituted or Mu置conversion of Fueeru group.  n represents 0 or 1. m, p and q each represent 0, 1 or 2, and when p is 2, two R ²⁴ may be the same or different, and when q is 2, two R ⁶ are each other. They may be the same or different. ) An acetylene derivative represented by the formula: 2 In the general formula (I), a phenyl group or an aromatic bicyclic group for R ¹ and R ² , a phenyl group or an aromatic heterocyclic group for R ⁷ and R ^8, and a phenyl group for R ¹³ When the fuel group represented by R ³⁹ , and R ³⁹ has a substituent, the substituent may be a halogen atom, a nitro group, a carboxyl group, a cyano group, an alkyl group, A C ₄ haloalkyl group, a di-alkoxy group,. ~. Haloalkoxy group, (C ₁ -C ₄ Anorekokishi) carbonyl group, an alkylthio group, Ci～C ₄ § Roh gravel Angeles sulfide El group and a C alkylsulfonyl, - acetylene of claim 1, wherein 1 or 2 groups selected from among Le group Derivatives. 3 The compound of the general formula (I) has the general formula (I-a)

(In the formula,! ^ ¹ to! ^ ⁶ , XX, Y, Z, and q are the same as described above.) 2. The acetylene derivative according to item 1, which is a compound represented by the formula: 4 In the general formula (I-a), X is

(Wherein, R ⁷ , R ⁸ and R ^1G are the same as described above.) And Y is a group represented by the formula

(In the formula, R ²⁸ , R ²⁹ , R ³¹ and R ³² are the same as described above.) And Z is a group represented by the formula One S one  0 m  (In the formula, m is the same as described above.) 4. The acetylene derivative according to claim 3, which is a group represented by the formula: 5 The compound represented by the general formula (I-a) is represented by the general formula (I-b), the general formula (I-c), the general formula (I-d), or the general formula (I-e) R ¹ — CC-CH — 0 R ³ — N (I-one b)  N, S (R ⁶ ) qo R.

^{(Wherein,! ^ ~ 8, R 10} , R 28 ~ R 32, X 1, m and q are the are the same as defined above) acetylene derivative according to claim 3, wherein a compound represented by the.  6. A herbicide comprising the acetylene derivative according to claim 1 and Z or a salt thereof as an active ingredient.