WO2004083193A1 - Amide compound and bactericide composition containing the same - Google Patents

Abstract

An amide compound represented by the formula (1-1): (1-1) (wherein X1 represents OR4 and Y1 represents hydrogen, or X1 and Y1 in combination represent =O or =NOR5; R1 represents hydrogen, halogeno, etc.; R2 represents hydrogen, halogeno, etc.; R3 represents C1-3 alkyl or C3-4 alkynyl; R4 represents hydrogen, C1-3 alkyl, or C3-4 alkynyl; and R5 represents C1-3 alkyl or C3-4 alkynyl). It is highly effective in controlling plant diseases.

Description

 Specification

 Amid compound and fungicide composition containing the same

 The present invention relates to an amide compound having a 5-membered nitrogen-containing aromatic ring in the amine moiety and a fungicide composition containing the same. Background art

 Conventionally, various compounds having a plant disease controlling effect have been developed, and many compounds have been put to practical use as an active ingredient of a fungicide composition, but the controlling effect may not be sufficient. Disclosure of the invention

 The present invention provides an amide compound (1)

[式中、 は、 下記の式 （A)、 （B )、 （C )、 (D) または （E )

[Where the is the following formula (A), (B), (C), (D) or (E)

X ¹ represents an OR ⁴ group, and Y ¹ represents a hydrogen atom. Table: f: or X ¹ and Y ¹ are taken together to form = 〇 group or = NOR ⁵ group R ¹ 'represents a hydrogen atom, a hydrogen atom, a C 1 -C 3 anolequinole group, a C 1 -C 3 haloalkyl group or a C 1 -C 3 alkoxy group; R ² represents a hydrogen atom, a halogen atom or C 1, or represents an C 3 Al 'kill group, or R ¹ and R ² are together a connexion, .. represent a trimethylene group, Note Toramechire emissions group or CH = CH- CH two CH groups; R ³ — Represents a C 1 :, C 3 alkyl group or a C 3 — C 4 alkynyl group, and R ⁴ represents water, a hydrogen atom, or “IT” represents a C, 3 alkyl group or a C 3 —C 4 alkynyl group; R ⁵ represents a C 1′-C 3 alkyl group or a C—C 4 alkynyl group. ^Γ "

(Hereinafter, referred to as the compound of the present invention). Three

[Wherein, X ¹ , YR \ R ² and R ³ represent the same meaning as described above. ]

, Amide compounds (1-2)

^{Wherein, XY \ R \ R 2,} R 3 and R ⁶ are as defined above. ] Amide compounds (1-1-3)

[Wherein, XYR \ R ² , R ³ and R ⁶ represent the same meaning as described above. ] Amide compounds (1-4)-

[Wherein, X ¹ , Y \ R \ R ² , R ³ and R ⁶ represent the same meaning as described above. ], Amide compounds (1-5)

[Wherein, X ¹ , Y ¹ , RR ² , R ³ and R ⁶ represent the same meaning as described above. ], Ryodo compound (1-6)

[式中、 は、 前記と同じ意味を表す。] 、 ァミ ド化合物 （ 1一 7 ) … 一

[Wherein, has the same meaning as described above. ], Amide compounds (1-7)

(1-7)

[式中、 R ¹、 R²、 R³、 R⁵

は、 前記と同じ意味を表す。] を提供する。 ―

Where R ¹ , R ² , R ³ , R ⁵

Represents the same meaning as described above. ] I will provide a. ―

The present invention also provides a fungicidal composition containing the compound of the present invention as an active ingredient and a method for controlling plant diseases, which comprises treating a plant or soil with an effective amount of the compound of the present invention. In the present invention, examples of the halogen atom represented by -R ¹ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and examples of the C 1 -C 3 alkyl group include a methyl group, an ethyl group and a Pill group and isopropyl group; and C1-C3 haloalkyl groups include fluoromethyl group, difluoromethyl group, trifluoromethyl group and 2, '22 -trifluoroethyl group, and C1-C3 Examples of T-lucoxy groups include: methoxy, ethoxy, and isopropoxy.

Examples of the halogen atom represented by R ² include a chlorine atom, a bromine atom and an iodine atom, and examples of the C 1 -C 3 alkyl group include a methyl group, an ethyl group, a propyl group and an isopropyl group. '-― ..

Examples of the C 1 -C 3 alkyl group represented by R ³ include a methyl group, an ethyl group, a propyl group and an isopropyl group, and examples of the C 3 -C 4 alkynyl group include a 2-propynyl group and a 1-methyl-2 —Provyl group, 2-butulyl group and 3-butynyl group; C 1 -C 3 alkyl group represented by R includes methyl group, ethyl group, propyl group and isopropyl group, and C 3 — Examples of the C 4 alkynyl group include 2-propynyl, 1-methyl-2-propynyl, 2-butynyl, and 3-butynyl. As the C 1 -C 3 alkyl group represented by R ⁵ , , Methyl, ethyl, propyl, and isopropyl. Examples of the C 3 -C 4 alkynyl include 2-propynyl, 1-methyl-2-propynyl, 2-butulyl, and 3-butynyl. And C 1—C 4 alkyl represented by R ⁶ Examples of the group include a methyl group, an ethyl group, and a propyl group. .. :: .- Embodiments of the present invention include, for example, the following compounds.

An amide compound wherein R ¹ is a hydrogen atom, a halogen atom or a C 1 -C 3 alkyl group in the formula (1);-In the formula (1), X ¹ is an OR ⁴ group and Y ¹ is a hydrogen atom there ami de compounds; in formula (1), X ¹ is a ^four 〇_R, Y ¹ is a hydrogen atom, an amino-de-compound wherein R ⁴ is a hydrogen atom;

In formula (1), X ¹ is OR ⁴ group, Y ¹ is a hydrogen atom, an amino-de-compound is 1¾ ⁴ Gazi 1 - ○ 3 alkyl group;

An amide compound in which, in the formula (1), X ¹ is an OR ⁴ group, Ύ ¹ is a hydrogen atom, and is an R ^ C 3 -C 4 alkynyl group;-· — In the formula (1), X ¹ is An amide compound in which OR ^{4 is a} group, Y ¹ is a hydrogen atom, and R ⁴ is a C 3 -C 4 alkynyl group;

In formula (1), X ¹ and Y ¹ are together ^{: an} amide compound having NO—R ⁵ groups; In formula (1), X ¹ and Y ¹ are together and = NOR ⁵ groups and the Ammi de compounds wherein R ⁵ is C 1-- C 3 alkyl group; ^"-:: in an equation (1), § R ¹ is a hydrogen atom - Mi de compound;

An amide compound wherein R ¹ is a halogen atom in the formula (1);-an amide compound wherein R ¹ is a chlorine atom in the formula (1);

An amide compound represented by the formula (1), wherein R ¹ is a C 1 -C ′ 3 argyl group;

An amide compound represented by the formula (1), wherein R ¹ is a methyl group;

An amide compound wherein R ² is a hydrogen atom in the formula (1);-an amide compound wherein R ² is a halogen atom in the formula (1);-an amide compound wherein R ² is a chlorine atom in the formula (1) Compound;

An amide compound represented by the formula (1), wherein R ² is a C 1 _C 3 alkyl group;

An amide compound represented by the formula (1), wherein R ² is a methyl group;

An amide compound represented by the formula (1), wherein R ¹ and R ² are taken together to form a trimethylene group;

In formula (1), R ¹ and R ² are joined together to form a tetramethylene group. Compound;

An amide compound represented by the formula (1), wherein R ¹ and R ² are joined together to form CH = CH—CH and H;

An amide compound wherein R ³ is a C 1 -C 3 alkyl group in the formula (1);-an amide compound wherein R ³ is a methyl group in the formula (1);

An amide compound wherein R ³ is an ethyl group in the formula (1); an amide compound wherein R ³ is a C 3 _C 4 alkyl group in the formula (1);

An amide compound of the formula (1) wherein R ³ is a 2-pro-butyl group;-in the formula (1), X ¹ is an OR ′ ¹ group, Y ¹ is a hydrogen atom, and R ⁴ is a hydrogen atom An amide compound that is

In the formula (1), X ¹ is an OR ⁴ group, Y ¹ is a hydrogen atom, and

Amide compounds that are 3 alkyl groups;

In the formula (1), an amide compound in which X ¹ is an OR ⁴ group, Y ¹ is a hydrogen atom, and R ⁴ is a methyl group;

In the formula (1), X ¹ is an OR ⁴ group, YV. Is a hydrogen atom, and R ⁴ is C 3— C

Amide compounds that are 4 alkynyl groups;

An amide compound represented by the formula (1), wherein X ¹ is an OR ⁴ group, Y 2 is a hydrogen atom, and R ⁴ , is a 2-pro-butyl group;

In the formula (1), X ¹ and Y ¹ are joined together to form a group of = NOR ⁵ -an amide compound in which R is a C 1 -C 3 alkyl group; In, X ¹ — and Y ¹ are taken together and — is NOR ⁵ group, and —: R ⁵ .: Is a methyl group; an amide compound;

In the formula (1), an amide compound in which X ¹ and Y ¹ are joined together to form a NOR ⁵ group and R ³ is an ethyl group;

In the formula (1), X) and Y ¹ together are = N〇R ⁵ groups, and R ⁵ -is C 3-

An amide compound which is a C 4 alkynyl group;:-. An amide compound of the formula (1) wherein X ¹ and Y ¹ are linked to each other to form a = NOR ⁵ group and R ' ⁵ is a 2-propyl group; Compound;.

In formula (1), an amide compound in which R ¹ is a halogen atom, and R ² is a hydrogen atom;: ·:-----.----In formula (1) An amide compound in which R ¹ is a chlorine atom and R ² is a hydrogen atom; an amide compound in which R ¹ is a bromine atom; and ² ′ is a hydrogen atom; In (1), an amide compound in which R ¹ is a CT-1 G-3 alkino group; and R ² is a hydrogen atom; ---. 1 '.-In formula (1), R ¹ is a methyl group. An amide compound wherein R ² is a hydrogen atom; an amide compound wherein R ¹ is an ethyl group and R ² is a hydrogen atom in the formula (1); In the formula (1), R ³ is a C 1 -C 3 alkyl group, X ¹ is an OR ⁴ group, Y 1 is a hydrogen atom, and R ⁴ is a C 3 -C 4 alkyl group Amide compound-;

In the formula (1), an amide compound in which R ³ is a methyl group, X ¹ is an OR ⁴ group, Y ¹ is a hydrogen atom, and R ⁴ is a C 3 —C 4 alkynyl group; · =; 5 In the formula (1), ¹ is a C 1-C.3 alkyl group; R ³ -is a C 1.-C 3 alkyl group; and X ¹ is a 〇R ⁴ group. An amide compound in which R ¹ is a hydrogen atom and R ⁴ is a G3—C4—alkynyl group; — —:. · ′ In the formula (1), R ¹ is C 1—G 3 a Anorekiru group, R ³ is a methyl group der Ri ■ ■ X ¹ is OR ⁴ group, Y ¹ is a hydrogen atom, - R ⁴ is C:.. 3- C'4- Arukieru group der

10 amide compounds;-·-: ':-

-In the formula (1), R ¹ is a halogen atom, R ³ is a C 1 -C 3 alkyl group, X ¹ is an OR ⁴ group, Y ¹ is a hydrogen atom, and R ⁴ is. An amide compound which is a 3-C-4 alkynyl group; + +--In the formula (1), R ¹ is a halogen atom, R ³ -is a methyl group, X ¹ is an OR 15 " ⁴ group An amide compound in which Y ¹ is a hydrogen atom and R ⁴ is a C_.3-C alkynyl group; —————

— ”In the formula (1), R ¹ is a C 1-3 alkyl group, R ² is a hydrogen atom, ¹ ! R ³ is a methyl group, X ¹ is an OR ⁴ group, and Y ¹ is hydrogen. atom -, and amino de compounds wherein R ⁴ is a C3 -C 4 alkynyl; -. '- Bruno -

20 In the formula (1), R ¹ is a methyl group, R ² is a hydrogen atom: R ³ is a methyl group—, X ¹ is an OR ⁴ group, Y is a hydrogen atom An amide compound wherein R ⁴ is a C 3 -G-4 alkynyl group;

-: · In the formula (1), R ¹ is an ethyl group, R ² : is a hydrogen atom, R ³ -is a methyl group-; X ¹ is an OR ⁴ group, and Y ¹ is a hydrogen atom Ami de compound is in and, R ⁴ is C3- C4 Arukini 25 Le group; ..,:. - -, - - - in formula (1), R ¹ is a halogen atom; -R ² two are a hydrogen atom -, 'R ³ is a methylcarbamoyl .. Le group, Y ¹ X ¹ is OR ⁴ group is a hydrogen atom, R ⁴ is C 3 - C 4 Al: Ami de is Kiniru group Compound; -

In the formula (1), R ¹ is a chlorine atom, R ² _ is a hydrogen atom, R ³ is a methyl group 30, X ¹ is an OR ⁴ group, Y is a hydrogen atom, An amide compound in which R ⁴ is a C 3 -C 4 alkyl group; ..-...--,-... '....: In the formula (1), R ¹ is a bromine atom R ² — is a hydrogen atom: R ³ — is a methyl group —, X ¹ is an OR ⁴ group, Y is a hydrogen atom, and —2 R ⁴ is C, 3 C 4 Alky: Amide compound which is a group; · ·. '..:--

In the formula (1-1), an amide compound in which R ¹ is a hydrogen atom, a halogen atom, or a C 1 C 3 benzoquinone group; An amide compound according to 1), wherein R ¹ is a hydrogen atom;

An amide compound in which R 'is a halo-gen atom in 1-1);-an amide compound in which R ¹ is a chlorine atom in 1-1);

1) The compound according to 1), wherein R ¹ is a C 1 -C 3 alkyl group;

In 1-1), - amide compounds wherein R ¹ is a methyl group;:. - - 1 - 1) - In Ammi卞R ² is a hydrogen atom; - '1 In one 1), R ² An amide compound wherein is a halogen atom;

In 1-1) —, an amide compound in which R ² is a chlorine atom ′; “In r-1-1), R ² is a C 1 -C 3 alkyl group;

An amide compound in which R ² is a methyl group in 1-1);.-An amide compound in which R ¹ and R ² are taken together to form a trimethylene group; ,

In the formula (1-1), an amide compound in which R ¹ and R ² are taken together to form a tetramethylene group;:-;-:

In the formula (1-1), an amide compound in which R ¹ and R ² : together form a CH = CH2 CH = CH group;

An amide compound of the formula (1-1) wherein R ³ ′ is a C 1 -C 3 alkyl group;

In the formula (1-1)-, an amide compound in which R ³ is a methyl group; 1.-In the formula (1-1),-an amide compound in which R ³ is an ethyl group; :

In the formula (1-1), an amide compound in which R ³ is a C 3 —C 4 alkyl group; in the formula (1-1), an amide compound in which R ³ is a 2-—propyl group; ': An amide compound of the formula (1-1), wherein X ¹ is an OR ⁴ group, Y ¹ is a hydrogen atom, and R is a hydrogen atom;---''-In the formula (1-1 1), ^An amide compound in which ¹ is an OR ⁴ group and Y ¹ is a hydrogen atom, and R is a C-C 3 alkyl group; 1-"-In the formula (1-1), X ¹ is an OR ⁴ group An amide compound wherein Y ¹ is a hydrogen atom and R ⁴ is a methyl group;-In the formula (1-1), X ¹ is an OR ⁴ group, Y ¹ is a hydrogen atom, and- An amide compound wherein R ⁴ is a C 3 -C 4 alkynyl group;

In the formula (1-1), an amide compound in which X ¹ is an OR ⁴ group, Y ¹ is a hydrogen atom, and R ⁴ is a 2-port butyl group; ...-a compound represented by the formula (1-1) -, X ^{1 and} Y ¹ are linked together: ": an amide compound in which R is a NOR group and R ⁵ is a -C 1 -C 3 alkyl group;:… '—: ~. In (1-1), an amide compound in which X ¹ and Y ¹ are joined together to form a group = NOR ⁵ and R ⁵ is a methyl group;...-: Formula (1-1) In the above, X ¹ and Y ¹ are linked together; NOR ⁵ groups, and R ⁵ is Amide compound which is a tyl group;-...;:-“·· — In the formula (1-1), X ¹ and Y ¹ are joined together to form a NOR ⁵ group, and R ⁵ is C 3 —C 4 alkynyl group amide compound · ..-—--: Γ-In formula (1-1), X ⁴ and Y ¹ together form = NQR ⁵ group, and R ⁵ -is 2 5 - amino de compound is flop pinyl group -; - r -:.. ...: -: -: in 'formula (1- ^1), R 1 is a halogen atom; der: Ri, R ² is hydrogen atom "der - Ru Mi: de compound; - ^ - ^-:.? - - - - in the formula (1 one 1), R ¹ is a chlorine atom, R force a hydrogen atom - in - Orua:卞..-::. — — One,....... 10 In the formula (i—iy, R ¹ is a bromine atom; and R ² is a hydrogen atom.

An amide compound in which, in the formula (1-1), R ¹ is a C 1. C 3 alkyl group, and R ² is a hydrogen atom; i In the formula (1-1), an amide compound 15 in which R ¹ is a methyl group and R ² is a hydrogen atom;-:.: +-';.:---:::-: In 1), an amide compound in which R ¹ is an ethyl group and R ² is a hydrogen atom:-one +...-

-In the formula (1-1), R ³ is a C 1 -C 3 alkyl group, X · ¹ is a QR ⁴ group, Y ¹ is a hydrogen atom, R ⁴ is a C 3 C 4 alkynyl group. In a formula (—1-1), R ³ is a methyl group, X ¹ is an OR ⁴ group, Y is a hydrogen atom, and R ⁴ is C 3 — C 4 ano: Amido compound which is a quinyl group----d. In the formula (1-1), R ¹ is a C 1 -C-3 asoalkyl group, and R ³ is An amide compound in which C 1 —C 3 alkyl group, X ¹ is OR ′ ¹ group, Y ^{1 is} S hydrogen atom, and R ⁴ is C 3 —C 4 — ′ alkynyl group; -· ■ · — '

25 In the formulas 1-1), R ¹ is a C 3 bull-quinole.- group, R: is a -methyl group, X ¹ is a 〇R ⁴ group, and Y ¹ is a hydrogen atom. And an amide compound in which R ⁴ is a C 3 -C 4 alkyl group-...;

In the formula (11-1), R ^{1 is a} halogen atom 1, R is a C 1 _′G 3 alkyl group, X ¹ is an OR ′ ¹ group, and Y ¹ is a hydrogen atom. Yes, an amide compound in which R ⁴ — is a C 3 -G 4 alkynyl group;----"to;-:-In the formula (1-1), R ¹ is a halogen ^: atom,- A mid compound wherein 'R ³ is a methyl group, X]-is an OR' ¹ group, Y ¹ is a hydrogen atom, and R ⁴ is: a C: 3-C 4 alkynyl group; -— · ',:-ノ —' In the formula (1-1), R ¹ is a C 1-— C 3 -alkynole group;; ² -is a hydrogen atom; and R ³ is a methyl group. An amide compound wherein X ¹ is an OR ⁴ group, Y ¹ is a hydrogen atom, and R ⁴ is a -C 3 -C 4 alkynyl group;:,--- In the formula '(1-1), R ¹ is a methyl group, R ² is a hydrogen atom, R ³ is a methyl group, X ¹ is an OR' ¹ group, and Ύ ¹ Is a hydrogen atom and R ⁴ is a C3-C4-alkynyl group;... 基 · '-, ·--In the formula (1-1)-, — R ¹ is ethyl R ² : is a hydrogen atom, —R ³ is a —methyl group; X ¹ is an OR ⁴ group, —Y ¹ ′ is a hydrogen atom, R ⁴ Is a C 3—C 4 alkynyl group: ·--■-.. .--..— — In the formula (—1-1—1), R ^{1 is a} halogen atom R ² is a hydrogen atom, R ³ — is a methyl group, X ¹ is an OR ⁴ — group, and 'Y' ¹ is a hydrogen atom '.

4 An amide compound which is an alkynyl group .-- ― In the formula (1-1-), R ¹ is a chlorine atom, R ² : is a hydrogen atom, R- ³ : is a methyl group, X ^An amide compound in which ¹ is an OR ⁴ group, .-Y ¹ is a hydrogen atom, and R ⁴ is a C 3 -C 4 alkynyl group;: — 1...: — In the formula (11), —— R ¹ is a bromine atom. R ² is a hydrogen atom. .. R ³ is a methyl group. X ¹ is a 〇R ⁴ group. Y ¹ is a hydrogen atom. ^ R ⁴ is a C atom. -3—G.4 Amide compound that is an alkynyl group.;.--:-:

In the formula (1-2) or the formula (13),-an amide compound in which R ¹ is a hydrogen atom, a halogen atom or a C 1 -C 3 alkyl group:: ..-;-'-'-Ninolevirazole compound of the formula (1-2) or the formula (1-13), wherein R¾ is a -C 1 -C 3 alkyl group;: --1-----2-. .::,-. In the formula (1-2) or the formula (1-13), a phenylvinylazole compound wherein R is a methyl group; "— · — —. _:.:-The formula (1-2) or the formula (1 I 3) Oh, and -R ¹ : a pheninolebi --- razol compound whose J is a child of the mouth; · 'V ¹ :

 • 5 In the formula (1-2) or (13), R is a chlorine atom.

In the formula (112) or the formula (113), R ² is a hydrogen atom-: eninolevirazole compound;-.-. — ⁷ ;:-Formula (112) ·. in the formula (1 one 3),: -.R ^2: "is: C: l ^'C: 3 is an alkyl group off ^10: Enirubirazoru compound; -:'

In the formula (1-2) or the formula (1-1-3-), -R ² -is a halogen atom in which -R2- is a ² -/-pyrazole compound;

In the formula (1-2) 'or the formula (1-3, R ⁶ is a C 1 -C 3 alkyl group. Compound;-.:.--;

15 In the formula (112) or the formula (113),-,: a pyrpyrazole compound wherein R is a methyl group;

In the formula (1-2) or the formula (1-3), a ferbilazole compound in which R ⁶ is a hydrogen atom;---...-.-The formula (1-2) or the formula (1-3) ) —, Wherein R ³ is a C 1 -C 3 alkyl group;

In the formula (112) or the formula (1-3), -R ³ -cameino group, a fenylvirazo mono-residence compound; ^^-'^- _:

--In formula (1-2) or in formula (13), X · ¹ is an O—R ⁴ group: a phenylpyrazole compound in which Y ¹ is a hydrogen atom and R ⁴ is a hydrogen atom ;--.-

25 In the formula (1-2) or the formula (1-3), X ¹ is an OR ⁴ group, Y ¹ is a hydrogen atom, and R ⁴ is a C 1 -C 3 alkyl group. Rubirazole compound;:-... In the formula (1-2) or the formula (1-3), X ¹ is an OR ⁴ group, ... Y ¹ is a hydrogen atom, and R ⁴ is a methyl group. Certain phenylvirazole compounds; ― '·

In the formula (1-2) or the formula (1-3), X ¹ is an OR- ⁴ group,-- ¹ is a hydrogen atom 30 and R ⁴ is a C 3 -C 4 alkynyl 5 group, that Fenirupirazo Le compounds; - in formula (1 2) or formula (1-3), X ¹ is a ^four Ό,: '' Y ¹ is a hydrogen atom, R ⁴ is 2-propynyl group - Oh 'Ru' Hue ≤ 'Lupira', pool ^; compound;-, in equation (1-2) or equation (1-3),-:. X ¹ and-Y together = NQR ⁵ Wherein R ⁵ is a C 1 -C 3 -alkyl group;

35 In the formula (1-2) or the formula (1-3), — X ¹ and Ύ ¹ ·-are taken together to represent the FNOR. ⁵ ′ group, and R ⁵ is a methyl group. Virazol 'compound .;- 'In Formula (1-2) or Formula (1-3), X ¹ and Y ¹ are joined together. = NOR ⁵ — represents a group, and R ⁵ is a C 3 —C 4 anorekinyl group. Rubirazone compound-;

In the formula (1-2) or the formula (1-3), X ¹ and Y- ¹ are taken together. = N.OR represents a ⁵ group, and R ⁵ is a 2-—prop'pinyl group. Ferruvirazole compound ― ―.-5 ^: -In formula (1 ^ 2) or formula (1-3), X- ¹ and. : —- “-:? Formula (1-2) Also, in Formula (1-3), R ¹ is a C 1 -C 3 alkino group; R ² is a phenylvinylazole compound which is a hydrogen atom

In the formula (1-2) or the formula (1-3), a phenylvirazole compound in which R ¹ is a tyl group and R. ² -is a hydrogen atom; — —.

'-Formula (1-2) or in formula (1-3), a phenylvirazole compound in which -R ^{1 is a} halogen atom and R ² is a hydrogen atom. —--- (1) 2) or a phenylvirazole compound represented by the formula (.1-3), wherein R ¹ is a chlorine atom and R ^2- . Is a hydrogen atom; In the formula (1-3), X ¹ is an OR ⁴ group, Y ¹ is a hydrogen atom, R ⁴ is a C 1 -C 3 alkyl group, and R ³ is a C 1 -C 3 alkyl group. -.:;- .::

In the formula (1-2) or the formula (1-3), 'X ¹ is a 〇R ⁴ group, Y ¹ is a hydrogen atom, R ⁴ is a C 1 -C 3 alkynole group, and R ^6- Is a hydrogen atom, and R ³ is a C1-20.G3 alkyl group; a phenylpyrazole compound;

-In the formula (1-2) or the formula (1-13, X ′ is a QR ⁴ group, Y ±. Is a hydrogen atom, and R ⁴ is a C 1—C 3 alkyl group. , R ⁶ is a methyl group, and scale ³ is 1- ■ -C 3 alkyl group phenylvilla ”sol compound ..;-:.-'-.-.

In the formula (1-1-2) or the formula (1-3), X ¹ is a 0_R ⁴ group, Y-shi is a hydroquinone atom: 25, R ^ C3—C4 alkynyl group. Phenylvirazole compounds which are C3-alkyl groups;

--.-. In equation (1-2) or equation (1-3):? : ¹ is an OR ⁴ group, Y ¹ is a hydrogen atom, R ⁴ is a C 3 -C 4 alkynyl group, R ⁶ is a hydrogen atom, R ³ is — C 1- ·-, A phenylbiazole compound which is a C'3 alkyl group;-30 in the formula (1-2) or the formula ( ^1-3 ), X ¹ is an OR ⁴ group; - and, R ⁴ is a C 3- C 4 Arukini ^ group, but be a methyl _group:, phenylalanine pyrazole compounds R3 is cl one C 3 alkyl group; -:. -: - - -.. A,. '-In the formula (1-2) or the formula (1 _ 3) —, R ¹ is <31.— a C3-alkyl group,

R ² is a hydrogen atom, X ¹ is an OR ⁴ : group-is, ： ¹ is a hydrogen atom,; R. ⁴ is a C.1-35-C 3 alkyl group, and R ⁶ is A phenylpyrazole compound that is a hydrogen atom;

In the formula (1-2) or the formula (1-13),-is a Halogon atom, and -R ² is water. X ¹ is an OR ⁴ 'group, Y ¹ is a hydrogen atom, v—R ⁴ is a —C 3 alkyl group, and R ⁶ is a hydrogen atom. In the formula (1-2) or formula (（3): R] C.1 is a C 3 -alkyl group, R ² is a hydrogen atom, and X ¹ Is an OR group, and: -Y ¹ -is a hydrogen atom, -A,--.R. ⁴ is a C 3 alkyl group, and -R is a methyl group. Zole compound;-. 'Formula (1-2) or Formula (1-3) is a hydrogen atom, R ¹ is a hydrogen atom, R ² is a hydrogen atom, and X ¹ is a hydrogen atom. R ⁴ group, 'Y ¹ -is a hydrogen atom, -R ⁴ is a G 1.—C 3 -alkyl group, and R ⁶ is a methyl group; -;---.. · In formula (1-2) or formula (1-3):-; R is CI.— C :: 3 alkyl group, and R ² -is a hydrogen atom. Yes -X ¹ is located in the OR ⁴ group are hydrogen atom, R ⁴ is C3 • one C 4 alkylene - a Honoré group, full E Rubira R ⁶ is a hydrogen atom - tetrazole compound;. -. Equation (1 — 2) or in the formula (1-3), —R ¹ is a halogen atom, R ² is a water: element atom, X ¹ is an OR ⁴ group, and Y ¹ is a hydrogen atom, A phenylvirazole compound in which R ⁴ is C3.—C4; an alkynyl group and R ⁶ is a hydrogen atom;

- or in the formula (1-3), ¹ - equation (1 2) 'is - a C U C 3 § / gravel group' ,, R ² is a hydrogen atom, X ¹ is OR ⁴ Motodea : R ¹ is a hydrogen atom ^ C;-a phenylvirazole compound in which R is a C 3 -C 4 alkynyl group and R ⁶ is a -methyl group; a formula (1-2) or a formula (-1-1 3), where R ¹ is -H-atom atom: R ·; R ² is -hydrogen atom, X ¹ is OR ⁴ group, Ύ ¹ is hydrogen atom, R ⁴ Is a 3 C4 alkynyl group, and R ⁶ is a methyl group.

-In the formula (1_2). Or the formula (1-3), .R ¹ ;-is a methyl group, and R ² is a hydrogen atom and R ³ is a methyl group. ■--In the formula (1-'2) or the formula (1-3), R is a chlorine atom ', R ² is a hydrogen atom, a hydrogen atom, and R ³ is Phenylpyrazole compound which is a methyl group; —-:.- ^:

In the formula (1-4) or the formula (1-: 5),-:: ¹ · is a chromium atom,:, a perogen atom or an amide which is a-C 1 -C. . compound; - Second, &: '-:' (1 one 4) or formula (1-5): Oite, _R ¹ is: C 1 -C 3 alkyl group der - Ru - off - 5 : '.::..; Including: · ·--A phenylazole compound in which R ¹ is a methyl group in the formula (1-4) or the formula (1-5). ;-;--:-::-.-';"

-In the formula (1-4) or the formula (1-5), R ¹ is a parogen atom, a .razole compound;-.-.--'_:. ) Or a formula (1-5) wherein R is a chlorine atom _:

'''-:-----:'-■ In formula (1-4) or formula (1-1-5), a vinyl alcohol compound in which R ² is a hydrogen atom .. .. .. J —: — ::: ·-.-.-: ■ pa ..-In formula (1-4) or formula (1-5), R ² is Gl- ^ C. 3-.. It is a rualkyl group. 5-.- ervirazole compound; "-.:.-·-· .- :: .... ..

In the formula (1-4) or the formula (1-5), R ^{2 is a} ha: logen atom, a pheninolebi lazonolai conjugate; π ^ ^; ■ '--"· The formula (1-4) or the formula (1— 5) In the formula, R ⁶ is a C 1 -C 3 benzyl group, or a enylvirazo compound of the formula (114) or the formula (1-5), wherein R ⁶ is a methyl group; :-.

In the formula (1-4) or the formula (1-5), a phenylvinylazole compound in which R ⁶ is a hydrogen thickener; .. —::...

Equation (1 4) or the formula (1 5) Oite ,,: - ³ CL- ^C: 3 ¾ a Rekiru group off 25 Enirupirazoru compound;? ^-· ^;; ..-A phenylvinylsol compound of the formula (1-4) or the formula (1-5), wherein R ³ is a methyl group;

In the formula (1-4) or the formula (1- ^ 5), X ¹ is an OR ⁴ group, and Y: ¹ is a hydrogen atom A phenylvirazole compound wherein R ⁴ is a hydrogen atom;:.--In the formula (14) or the formula (1-5), X ¹ is an OR ⁴ group, Y ¹ is a hydrogen atom, and R ⁴ is a C 1 C 3 alkyl group Hue Rubirazoru compound; -V-:.. in formula (1-4- or formula (1- 5) ·, -X ¹ is oR ⁴ group, Upsilon · ^ is A phenylvinylazole compound having a hydrogen atom 5 and R ⁴ being a methyl group; ...:-;---·: In the formula (1-4) or the formula (1-5), X ¹ is 0 . be a scale ⁴ ¾, -Y ¹ is a hydrogen atom - and -, R ⁴ is C3- C4 alkynyl ¾ full sulfonyl 'Vila:. / Lumpur compounds; - - - - two - equation (1 4 ) Or in formula (1-5), wherein X ¹ is OR ⁴ 、 and Y ¹ is a hydrogen atom ^: and a phenylpyrazole compound wherein R ⁴ is a 2-propynyl group;

: 10 Formula (1-4) or -Dara formula. In (1-5)-, X ¹ ... and Y ¹ are linked to each other: = N OR represents ⁵ groups, and R ⁵ is C 1 . -C is a 3 alkyl group off - E two Rupirazo Le compounds - formula (1 4) or the formula (1 5) in, X ¹ _and: Toga cord in summer r:. = NOR_ ⁵ - - group And R ⁵ is a methyl group, a ferrule compound; · ·. ”—.-In the formula (1-4) or the formula (1-5)., —X ¹ and Y are taken together -Represents = NOR ⁵ "15 groups, and ⁵ is a C3- (34 alkynyl group) compound; r In the formula (1-4) or the formula (1-5), X ¹ and A furubirazole compound in which Y ¹ -and: are linked to each other to represent a NOR- ⁵ -group, and R ⁵ is a 2-propynyl group

In the formula (1-4) or the formula (1-5), -R ¹ C.1.—C 3 -alkyl group, and -R ² is a hydrogen atom. :

20 In the formula (1-4) or the formula (1-5): where R ¹ is a tyl group, and -R. ² is a phenylvirazole compound having a hydrogen atom-.;:. -·-.-.;-

, ■ In the formula (1-4) or the formula (1-5), a phenylvinylazole compound in which R ^{1 is a} halogenogen atom and R ² is an ice atom-.

-In the formula (14) or the formula (1-5): a phenylvirazole compound in which R ¹ -is a chlorine atom and R ² -.— is a hydrogen atom;

In the formula (1 4) or the formula (15), X ¹ is a QR ⁴ group: Ύ ¹ -is a hydrogen atom. R ⁴ is a CI—C3 alkyl group— and R ³ is a CI— C-alkyl phenyl virazole compound::.: .- .. ■: / ■ .: One-one:-

In the formula (1-4) or the formula (1-5), X ¹ is an OR ⁴ group, Y ¹ is a hydrogen atom 30-, R ⁴ is a C 1—C 3 alkynole group, and —R There is a hydrogen atom,: - Contact: ³ I one - Fuenirupirazo Les female compound is C 3 alkyl group; - equation (.1 4) or the formula (1 5):.., X ¹ is QR ⁴ - Motodea; Y. ^ is hydrogen atom - and, R ⁴ is a C 1-C 3 alkyl radical, R methylcarbamoyl - a Le group, R- ³ is C 1-

-C 3 alkyl group.Vinyl villa: .Zole compound-:; ·.;-.. ·---:::,-■---- V. 35 Formula (1-4) or Formula (1 — In 5), ^ ¹ is an OR ⁴ group, Υ ¹ · is a hydrogen atom---, R ⁴ is a C 3 _ C 4 alkynyl- group, and R- _; ³ is .. G 1, C-3 alkyl group Phenylvirazole compound;; V · '·.--.-· .— · · ·

-.. In the formula (1-4) or the formula (1-5), X ¹ is an OR ⁴ -— group, U… is a hydrogen atom •-, and the shaku ⁴ is a 3- to 4-alkynyl group. In this formula, ⁶ is a hydrogen atom, and ³ is a 1- — -—— C 3 alkynole group. In the formula (4) or the formula (1-5), X ¹ is an OR ⁴ group, Y is a hydrogen atom ′, R ⁴ is a C 3 -C 4 alkynyl group, R ⁶ is a methylol group and R Phenylbitazole compound wherein ³ is a C-1 to C3 alkyl group;- ^: -no: no —

- "formula (1 4) or the formula (1-5-), R ¹ is located at € 1- C 3 alkyl group. R ² is a hydrogen atom, X ¹ is OR ⁴ group, Y ¹ Is a hydrogen atom, R ⁴ is a C 110-: one G3 alkyl group, and R ⁶ ; is a hydrogen atom, a ferpyrazole compound ';'--formula (1 4)-or formula (1-5 ), Is a halogen atom; R ² is an ice atom, X ¹ is an OR ⁴ group—, Y ¹ is a water-hydrogen atom—, and R. ⁴ is C-1— A furpyrazole compound having a C 3 alkyl group and R ⁶ being a hydrogen atom;-.z '----In the formula (14) or the formula (1-5), R ¹ is C 1: .— a C 3 alkino group .: 15 R ² is a hydrogen atom, X ¹ is an OR ⁴ group, is a hydrogen atom, and one R is Cl:

'· .—C 3 alkyl group and R ⁶ is a methyl group.

In the formula (1-4) or the formula (1 5), R ¹ - is a halogen atom, "R ² - is water atom, X ¹ is a ^four 〇_R, Y ¹ is is a hydrogen atom, R. ⁴ is C .1- C 3 § alkyl group, Hue Rupirazoru R ⁶ is methyl group; - 20 '& - formula (1 4) or the formula (1 one 5) in, R ¹ is C 1 one C .3 alkyl group, R ² is a hydrogen atom, X ¹ by OR ⁴ group - Yes, - -Y one ¹ - a hydrogen atom located;. R ⁴ is A phenolic compound having a C 3 -C 4 alkynyl group and R ⁶ being a hydrogen atom;: In the formula (1-4) or the formula (1-5), R ¹ is a halogen atom; R ² is a water atom, X ¹ is a 〇R ⁴ group, Y ^1. Is a hydrogen atom :, R ⁴ is a C.3—C 4; α 25 norekinyl group, and R ⁶ is a hydrogen atom Atomic phenirazole compounds.

In formula (1 _ 4) or formula (1 _ 5), -R ¹ is a C 1 C, 3 alkino k group;, is a hydrogen atom, X ¹ is OR ⁴ , Y ' ¹ is a hydrogen atom, R. ⁴ is a C3: 1 C 4 alkynyl group, and R- ⁶ is a ^ tyl group. — In 4) or in formula (1-5), R ¹ is a halogen atom,. R ² is a hydrogen atom, X ¹ is an OR ⁴ group, and is hydrogen. R ⁴ is a .G—3 C 4 flexyl group, and R ⁶ is a methyl group, a fuel pyrazole compound “, — in the formula (1-4) or the formula (1-5): -R ¹ is a methyl group, R is a hydrogen atom, and R ³ is a methyl group.

-In the formula (I-4) or the formula (1-1 5) ', -R] is a chlorine atom. ... R ² is a hydrogen atom. _ 35 · a phenirvirazole which is a methyl group and R ³ is a methyl group. Compounds;-.. „一

: In the formula (1-6), R ¹ is a hydrogen atom, ^^-one ^ or Cl—C 3 alkyl ^ group. A: Compound; -no-:---:: to '-- :: Formula (in 1-6;-: is a hydrogen atom. A: Mido compound; --—::-:: Formula (In the formula 1-16, R ¹ force ^, mouth-da atom In the formula (1-6, R ¹ is a chlorine atom: an amide compound;-;--:--:-. In the formula (1-6, ^An amide compound in which ¹ is a C-1C.3 alkyl group-;-· (1 to 6 in which R1 ^: is a methyl group and a amide compound :; (in 1-6, R ² - is a hydrogen atom ami compound;:.. .. -: - -: Bruno '■;■' in formula (1-6, R ² Gaha port: a Gen atom Ryo Mi de compounds:;.... - ::: - in formula (1-6, - amino de compound wherein R ² is a chlorine atom;, · ■ - ■ the formula (1-6 There are, ami de compound wherein R ² is a C 1-C 3- alkyl group; -:.. .. - in formula (1 -6, an R ² turtles les group ami compound;: - - - -In the formula (116, an amide compound in which-R ¹ and-are together and are a small lylene group:

In the formula (1-6, R ¹ and R ² ′ are ¾, あ る ^ -α.

. In the formula (1- 6., R ¹ and R ² and are cord: the Do: connexion OH = - ami de匕合was a H ^ GH = CH group;.

In the formula (1-6, R ³ is C 1; -C 3 -alkyl group: 'a. Amide compound-; In the formula (1-6-, R ³ is a methyl group. ;-

In the formula (1-6), an amide compound in which R ³ is an ethyl group ■ :: · In the formula (1-6, an amide in which R ³ is a C 3 C 4 alkynyl group Compound;--Formula (1-6, wherein R ³ is 2-pyrole; amide compound;-"--- Formula (1-6 ', R ^{1 is} Is a gen atom :: り ';:.: R- ² is a hydrogen atom:

'In formula 1-6, R is Oh chlorine atom: _ ._, -' Ami compound is R force ¾7j rather atom; - - in formula (Γ_6, R ¹ is a bromine atom, - R ² Is a hydrogen atom- Thing; ':-: .. ·'

'In the formula (1-6), R ¹ is a C 1 -C 3 alkyl group, and R ^2- ' is a water "^ atom. Amid compound;-·.-:. In the formula (1-6), R ¹ is a methyl group,--, and R ² is a hydrogen atom. Amidated food.-I.---..; Nino---· Formula U- in 6), - R ¹ is E Ji Motodea -:. Ri, - "R ² hydrogen atoms, § Mi de compound is a child; ^ i .: --- r- ';'·; - - "■ '-

In the formula (1-7, an amide compound in which R ¹ is a hydrogen atom. — ■ .. ^{; In the} formula (1-7, an amide compound in which R ^{1 is a} rho or rhodan atom;

In the formula (117, an amide compound in which R ¹ is a chlorine atom .; —. V ·:-:...

(-1 one 7 - In, R ¹ is C 1-C 3 alkyl group der Ru ami .. de compound;..., Formula - (in 1-.7, 'R ¹ is an Mechizore group ami - de compound:; - 'formula (1 7. in ^, ami de R ² is a hydrogen atom:;.... _, ^ - equation - (1 - at 7, R ² Ganoderma, androgenic atom In the formula (117, an amide compound in which R ² is a chlorine atom;- ^; -.. In the formula (1-7, R ² is C 1 An amide compound that is an alkyl group;

In the formula (1-7, an amide compound in which R ² is a methyl group-; ':-· ■ -...-: ..-,-: In the formula (17, R ¹ R ² And an amino compound which is a methylene group;

In the formula (117), R ¹ and R ¹ together form a tetramethylene group:

In the formula (17, R ¹ and C H ′ = C Hi-;

A certain amide compound; r:-1 ';---;--^ Formula (In 1_7, R ³ is a C 1 C .3 alkyl group. In the formula (117, an amide compound in which —R ³ is a methyl group;:-:. In the formula (1-7, an amide compound in which R ³ is an ethyl group :;. An amide compound wherein R ³ is a C.3-4 alkynyl group in the formula (17); an amide compound wherein the R ³ is a 2-zulovinyl group in the formula: '- In the formula (17), an amide compound in which R ¹ is a halogen atom and R ² is a hydrogen atom;

■ In the formula (1-7), an amide compound in which R ¹ — is a chlorine atom and R ² is a hydrogen atom;

5. In the formula — (1-7), an amide compound in which R ¹ is a bromine atom and R ² is a hydrogen atom;---: '-■--:. — 7) In the amide compound, wherein R ¹ is a C 1 -C 3 alkyl group and R ² is a hydrogen atom;

-. In the formula-(1-7), an amide compound in which R ¹ is a methyl group and -R ² is a hydrogen atom;-.--::.

• In the equation (1 one 7-), R ¹ is located at Echiru group ■ - ami de R ² is a hydrogen atom: compound - things like - ₀ -.:

Clarify the method for producing the compound of the present invention '

5 The compound of the present invention can be produced, for example, by the following production methods 1-3. Manufacturing method 1-.---:-

-Among the amide compounds (1), the compound (1-1a) can be produced by reacting the compound (2) with the compound (-3) in the presence of a base. ------

0 (3) (1-a

[Wherein X ¹ — ¹ represents OR ′ ¹ — ¹ group, Y ¹ — represents a hydrogen atom, or a certain V, with X:, Y ¹ —— represents N_〇_R ⁵ group, R ⁴ -. ¹ represents a C 1-C 3 alkyl group or C 3- C 4 alkynyl ^{group, RR 2, R- 3, R} 5 and

5 has the same meaning as described above. ]

-The reaction is usually carried out in the presence of a solvent < Examples of the solvent used in the reaction include ethers such as tetrahydrofuran, ethylene glycol dimethyl ether and tert-butynolemethyl ether; aliphatic hydrocarbons such as hexane, heptane and octane; and aromatic carbons such as toluene and xylene. I-Daisui-. Primers, halogenated hydrocarbons such as benzene, etc., esters such as butyl acetate and ethyl acetate, nitrites such as aceto-nitrile, -N, N: -dimethylform _: Acid-amides such as amides; sulfoxides such as dimethyl sulfoxide and mixtures thereof. '"-:-:--Bases used in the reaction include sodium carbonate, carbonated lime and the like: genus carbonates, triethylamine, -diisozu. Pyrethylamine, 1, 8: Tertiary amides such as diazabi 10-cyclo [5,4, Ό] pentadiene 7-ene, 1,5-diazabicyclo [4,3,0] non-5-ene and pyridine, 4-dimethylamizo And nitrogen-containing aromatic compounds such as pyridin.

 The compound (3.) is usually in a ratio of 1 to 3 mol, and the base is usually in a ratio of 1 to 10 mol, per 1 mol of the compound (2). -: :: '.-.:::-:.

15-The reaction temperature of the reaction is usually in the range of 20 to 10 hours, and the reaction time is usually in the range of 0.1 to 24 hours. — — —

 After completion of the reaction, the reaction mixture is extracted with an organic solvent, and the organic layer is subjected to post-treatment operations such as drying and concentration, whereby the compound (1-a) can be isolated. You. Isolated compound (1-al is purified by chromatographic chromatography, recrystallization, etc., and can be further purified. 20: Can be obtained.---:-.--- 2 --- --- Amide compound (1) can be produced by reacting compound (4) with compound (5) in the presence of a base.

25 ( ⁴ ) ( ¹ )-

[In the formula, L ¹ -represents a chlorine atom, a bromine atom or an iodine atom, and RR ² , R ³ , X ¹

-γ ¹ and ■. '-

 Represents the same meaning as described above. -.-.-ノ-.:-.

-The reaction is usually performed in the presence of a solvent. '. ·.:-. -D---: Solvents used in the reaction include, for example, tetrahydrofuran, ethylene glycol

5 Noredimethyl ether, tert-butyl ether: ethers such as ether: aliphatic hydrocarbon dioxane such as xane, heptane and octane; aromatic dihydrogens such as -xylene Halogenated hydrocarbons such as benzene and the like; butyl acetate; esters such as ethyl acetate; nitriles such as acetotrile; acid amides such as N-di: methylformamide; Sulfosides such as dimethylsulfoxide and mixtures thereof are included. -One::-:.

As the base used in the reaction, for example, Nato carbonate!ゥ: Alkali metal carbonates such as potassium, potassium carbonate and the like; and alkali metal hydrides such as sodium hydride and the like. :: 1 mole of compound (4), 1 mole of compound (5 moles, usually 12 moles, salt: group usually:! ~ 2 moles.... ..,.: _> :. _

15 The reaction temperature of the reaction is usually in the range of 1 to 2040, and the reaction temperature is usually in the range of 0.1: 1 to 24 hours. . .. - - /·' Man . .· - , ,:

-After completion of the reaction, the amide compound (1) can be isolated by performing post-treatment operations such as extracting the reaction mixture with an organic solvent and drying and concentrating the organic layer. The isolated amide compound (1) can be further purified by chromatography, recrystallization or the like. --.: ■-.:-'--: Manufacturing method 3---

The amide compound (1) can be produced by reacting the compound (6) with the compound (3) in the presence of a dehydrating condensing agent. '·-: ... one->one-'

I: wherein R ¹ , R ² , R ³ , X ¹ , -Y ¹ and

 -Represents the same meaning as described above. The reaction is performed in the presence of a common solvent. --…--: · ·

'Examples of the solvent used in the reaction, for example N, N-dimethylformamide §' acid Ami 'single 5 such as Mi-de - frequent de, dimethyl sulfoxide and the ^like: sulfoxides ,, pyridine, nitrogen-containing, such as quinoline - aromatic Compounds and mixtures thereof. "-Hen- ':: The dehydrating condensing agent used in the reaction is ェ -ethyl-3- (3-dimethylano- ^: propyl) garbodiimid hydrochloride, 1,3-dicyclohexyl- -'- "carbodiimides such as force / repository. , ":.-,. —

10 Compound (3) is usually in a ratio of 1 to 3 mol, and a dehydration condensing agent is usually in a ratio of l to 5 mol per mol of compound (6). : "---.,--■

'-: The reaction temperature of the reaction is normal. To 1-4 in the Q ^P C Me range song - Oh -. Is, the reaction time is usually! ; To 24-: Time range. —. ■-: · ..-.:.

: After completion of the reaction, the reaction mixture is filtered, and ^: After-treatment such as extraction of the conc. Liquid with an organic solvent, drying of the organic layer and concentration of -15 is carried out. (1) can be isolated. -The amide compound (1) used is:

- ^: Can be further purified. — ノ ■:. "·: '...:-^. .. Production method 4:.;-.-

The compound (1-d) can be produced by reacting the compound '(1-C) with an acid. -ノ _

 (1-c) _, (1-d)

^; Wherein, R ⁹ represents a tert- butyl ^{group, X 1, Υ 'R 1} R 2, - ^ 3 "ho same meaning as above -: represents the taste, -

 Is shown below

-Represents one of I., ::::::; '.:. Pa.- -.'-.': .-: The reaction is carried out in the presence or absence of a solvent. •: Solvents used in the reaction-include, for example, alcohols such as methanol and ethanol, organic acids such as acetic acid and propionic acid, dihydrate, and mixtures thereof. Examples of the acid used in the reaction include, for example, inorganic acids such as hydrochloric acid and sulfuric acid. The acid is usually 1 mole of the compound (1 _ c) .. Ό -1 ^: mole to excess amount J ·--The reaction temperature is usually 0 to 1-Ό ° C The reaction time is usually from 0 to 1

'24 hours range. --… Two-, ■, ■ ■ · ■.--; V: .-:;

 After completion of the reaction, the compound (1d) can be isolated by extracting the reaction mixture with an organic solvent and performing post-treatment operations such as concentration of the organic layer by drying. The isolated compound ^ (1-1d) can also be roughly purified by chromatographic τ-: recrystallization or the like. -:-Production method 5 'S--'--,.-Compound (8) can be produced by -reacting compound (7) with: ...

(Where RR ² , R ³ and

 Represents the same meaning as described above. ] ...--_-'---.

 • The reaction is usually performed in the presence of a solvent. --The solvents used for the reaction are, for example, methanol, ethanol, 2-propano

5-alcohols such as 1,4-dioxane, tetradrophthene, ethylesciglycol di-methyl ether,-tert-butylinolemethyl ethers, etc., aliphatics such as hekisan, heptane, octane, etc. Hydrocarbons: 'Aromatic hydrocarbons such as toluene and xylene, 7k and mixtures thereof. ···: ^; : '-— "ー Examples of the reducing agent used for the reaction are' titanium borohydride and 'hydrogenated borohydride.

Potassium potassium. · - ■ ^·:: One '-' - - Compound (7) with respect to 1 mol of the reducing time is usually a proportion of 0 .. '25-2乇Ru. . - - reaction 'temperature of the reaction is usually in the range one. 20 to 100 ^{9 C,:} usually instantaneous if the reaction time - in the range of 24 hours. Λ ''.-:-"-----^

-After the completion of the reaction, the reaction mixture is concentrated under reduced pressure, extracted with an organic medium by adding ice, and the organic 15 layer is dried and concentrated to isolate Compound (8). -You can. 'The isolated compound (8) can be further purified, for example, by chromatographic recrystallization. '-—' ―- ^: ^ ■--; ~ ..: Manufacturing method 6-

20 Compound (12) can also be produced by the following method.

.

.

 Represents the same meaning as described above. -Compound (10) can be produced by reacting compound (9)-with methanesulfonyl chloride in the presence of a base. ,--:::-::-,--

The reaction is usually performed in the presence of a solvent. '.-Examples of the solvent used in the reaction include ethers such as 1,4-dioxane, tetrat-drofuran, ethylene glycol dimethyl ether and tert-butyl methyl ether, and aliphatic hydrocarbons such as hexane, heptane and octane. Aromatic hydrocarbons such as toluene, xylene, halogenated hydrocarbons such as benzene benzene, esters such as butyl, butyl, and ethyl acetate; nitriles such as acetonitrile; N, N-dimethylformamide And the like, sulphoxides such as dimethylsulfoxide, and mixtures thereof. --. Examples of the base used in the reaction include carbonates such as sodium carbonate and potassium carbonate, metal hydrides such as sodium hydride, triethylamine, disopropylethylamine, 1,8-diazabicyclo [ 5.4.0] Pendek 7-ene, tertiary amines such as 1,5-diazabicyclo [4.3.0] non-5-ene and pyridine and 4-dimethylaminopyridine And nitrogen-containing aromatic compounds. Methanesulfonyl chloride is usually in a ratio of l to 3 mol, and a base is in a ratio of 1 to 10 mol per 1 mol of compound (9).

 The reaction temperature of the reaction is usually in the range of 120 to 100 ° C, and the reaction time is usually in the range of p. 1 to 24 hours. ·: ...-

5 After completion of the reaction, the compound (10)-can be isolated by subjecting the reaction mixture to extraction with an organic solvent, drying, and subjecting the mixture to post-hypertrophy processing. — The isolated compound (10) can be further purified by chromatography, recrystallization, or the like. 'Compound (1-2) can be reacted with compound (10) and compound (11).

10-Can be manufactured. ; - human -:. ^'-, .. - the reaction is the presence or absence of a solvent, Ru performed in base © absence or presence. -----.-:--/

-Solvents used for the reaction include, for example, 15 ethers such as 1.4 dioxane, tetrahydro-furan, ethylene glycol di-methyl ether, tert-butyl methyl ether, hexane, -Aliphatic hydrocarbons such as heptane, octa: etc .; aromatic hydrocarbons such as ren, noki ... silene, etc .; acetate Bed chill, nitriles such esters Asetonitoriru such as acetic Echiru, N, ..N- dimethyl _ Chiruhorumuami de like acids § Mi:. earths ^ Oyo sulfoxides such as methyl _sulfoxide: beauty of these mixtures Is raised. · ■ '·-'-―--20-Examples of bases used in the reaction include carbonic acid salts such as sodium carbonate and potassium carbonate, anolyte metal hydrides such as sodium hydride, and triethylamine and diethylamine. Isopropylethylamine, 1,8-diazavicik mouth [5 · 4.0] Pin-de: Zuk 7.1, 1, .5-diazavicik mouth [4.3.0] non-5—d These include tertiary amines such as ^ _: mins-and pyridine, 4-dimethylaminopyridine, etc. Nitrogen-containing aromatic compounds. -:.; '-· +.--.:?…:'.-Compound (11) is usually in the range of 1 mol to excess in relation to 1 mol of compound (10). The base is usually in a ratio of 0:! To 5 mol. · · · —-'---■ The reaction temperature of the reaction is usually in the range of 0 to 150 ° C, and the -reaction time is usually in the range of 0.5 to-, 24 hours. · · · · · _.- , · ■ _{: ¾} - _:: -

After completion of the reaction, the compound (12) can be isolated by performing post-treatment operations such as removing the organic solvent from the reaction mixture and drying. The isolated compound (1 '-. 2) can be further purified by chromatography, recrystallization, etc. ——— Next, a method for producing an intermediate for producing the compound of the present invention will be described. ·-

35-Intermediate production method 1.--

:' ( 2-a.) ：- . .

: '(2-a.):-.

- wherein, R ⁸ situ methyl group or Echiru group - Table, Ms. is a methanesulfo two Le group table - ^{and, - R \ R 2 -,} R 4 - 1 is the same meaning as described above roughness:. Wath The compound (22) can be produced by reacting the compound (21) with hydrogen. Boron sodium and-.

 The reaction is usually performed in the presence of a solvent. ':-

-Examples of the solvent used in the reaction include: alcohols such as ethanol, ethanol, ethers such as tetrahydrofuran, and mixtures thereof. ... The ratio of hydrogen sulfide / hydrogen sodium is usually from 0. -25 to 2. mol based on 1 mol of compound (21) -1. :---: .. '---: • The reaction temperature of the reaction is usually in the range of 20 to: 5.0: ° C, and the reaction time is usually in the range of instantaneous .-2.4 hours. After the reaction is completed, the reaction mixture is concentrated, water is added, the organic solvent is extracted, and the organic layer is dried and concentrated. Compound (22) is isolated: The isolated compound (22.) can be further purified by an operation such as chromatographic recrystallization. Compound (2'3) can be produced by reacting compound (22) 'with chloride: methans ^: honyl in the presence of a base. · —--.-.:

: '-The reaction is usually performed in the presence of a solvent. Solvents used in the reaction include, for example, tetrazole; ethers such as tetraphenyl-co-ter, ether, tert-butylin-co-terether, hexane,

Aliphatic hydrocarbons such as -butane, -octane, and aromatic hydrocarbons such as toluene N, N-N-dimethylformamide and other acid amides, dimethyl sulfoxide, etc.? ) Slefoxi. H: Kind and the 5 'compound are lost. +-':::''_-; Bases used in the reaction include, for example, sodium acid carbonate, carbonic acid lime, etc. <alkali .5' Potassium metal carbonates, triethyleamine, diisopropylethylamine, 1 8 pages--azabicyclo [5,4,0] —index 7 _ 1, 1-, 5 _: diaza: seven, six-[4, no-.3, 0] non — 5 —N-containing aromatic compounds such as tertiary amines such as -ene and pyridine, and: 4-didimethylami-nopi-lysine. ^-:. ■: _ '^

 --Compound (22). The amount of methanesulfonyl chloride is usually 1 to 3 moles per 10 moles, and the base is usually 1 to 0 moles. ―--ノ-

The reaction temperature of the reaction is usually in the range of −20 to 100 ° C., and the reaction time is usually in the range of 1 to −24 hours. -.. To the second. ·-,,--

After completion of the reaction, compound (23.) can be isolated, for example, by performing a post-treatment operation by the following method.

 Extract the 15 ". (.I) reaction mixture with an organic solvent; dry the organic layer: and concentrate it.

 "(ii) Filtration of the reaction mixture '; concentration of the filtrate-method ....' ^:--_.: ·-: .-.:.;,--The isolated compound (1.3 ) Can be refined to Croat: Graph, Recrystallization, etc. by operations such as:-:-:.

20 Compound (-25) can be produced by reacting compound (23) with compound ((2ΦΦ). ... '. R ...:' 2-:

 : The reaction is performed in the presence or absence of a solvent.;-!.,: '.-:,

-Examples of the solvent used in the reaction include 1-,-· 4 _: · dioxane, -tetra_hydrofuran -.- ethylene glycol-dimethyl eno ^-, er ^ buty ^^^ C¾25 Athenoles, hexane, heptane, octane, etc .; aliphatic hydrocarbons, aromatic hydrocarbons such as toluene, xylene, etc .; .- nitriles, such as nitrile; N, .N-di'-tilform ', etc .: acid amides:, ..; jetty:. Sulfoxides, such as sulfoxides, and mixtures of these _: Compound-(2.4 :) is usually in an amount of 1 mol to excess in relation to 1 mol of compound (23). The reaction temperature is usually in the range of 50 ° C to 1.50 ° C, and the reaction time is

Range of 24-hours. ; _ _: ;;; r- ;.-After the reaction is completed, the reaction mixture is concentrated in organic solvent H ^, and the concentrated layer is dried and concentrated. As a result, the compound (25) can be isolated and purified by an operation such as chromatography and recrystallization. …--":-One-.

-'+ ——1 ¹ "■---~ ·· ^k ·. 2— ^---'- Compound (26) can be prepared by 'reacting compound (25) with water in the presence of a base'. - ^: -τ-. _ The reaction is usually carried out in the presence of water and an organic solvent. - - Bruno ... The organic solvent used in the anti-^, such as methanol, .. ethanol Al ^of: co Lumpur acids, as tetrahydrofuran, gamma, 4-di * hexa: such emissions instantiation: ethers And mixtures thereof. : + '- - - "- ' - ■ Examples of the base Chi used in the reaction include hydroxide ^Richikemu:. Sodium hydroxide: such oxidizing power Riumu Al force Li metal hydroxides there: Chireru .. ··· ': · ·' -—.-V.

-Compound (25) The base is usually: ~ 2; 0: The ratio of things. The reaction temperature of the reaction is usually in the range of 0 to 100 ° C .: The reaction time is usually in the range of -0-:-'5 ^ -24 hours.--.-- After completion of the reaction, the reaction mixture is mixed with an acid (for example, an inorganic acid such as hydrochloric acid) to make the mixture acidic, and then subjected to a post-treatment operation such as extraction with an organic solvent, drying and concentration, thereby obtaining a chemical compound. The isolated compound '. (26)' can be further purified by an operation such as chromatography and 5-recrystallization. :------:-

- ^: -Compound (2-a) can be produced by reacting compound (26)-with thiol chloride. No —— ———--

-The reaction is carried out in the presence or absence of a solvent. The solvents used in the reaction include, for example, chloro: .. mouth: -halogenated hydrocarbons such as benzene, aromatic compounds such as toluene and xylene, and mixtures thereof. Is raised.

'-Compound (26) 1 mole of compound (26)

--.: The reaction temperature is usually in the range of 20 to Γ00 ° C., and the reaction time is usually in the range of 0.5 to 5: 5 to 24 hours. ----- — .. ..-; After completion of the reaction, the compound: (2-a) is isolated by performing post-treatment operations such as concentration of the reaction mixture. _{compound 5} was isolated play that can be (-2-a) - is the distillation: I - can be Risarani purification. -----------------------

(22) (27) In the formula, .RRR ⁸ has the same meaning as described above. - ^.;

'Compound (27) is prepared by reacting compound (25.) with compound (22) instead of compound (25.) according to Intermediate Production Method 1 (Steps 11-14). - :it can. -—.:.-·-. ·.--.. Intermediate production method 3

- ： - 化合物 （3 3) は、 化合物 （2 Γ) と—化合物 （3 2) とを反^きせることにより- 製造することができる。 ： ： -— - —- - - -·· - :'-― ：

-:-Compound (33) can be produced by reacting compound (2 （) with-compound (32). ::----------: '-

- Compound (3 2) compound represented by the - for example the hydrochloride and salts or ^sulfate: with ^D: - ^ when standing can also i- using a salt thereof to reaction. · '— —--The reaction is usually carried out in the presence of a solvent, in the presence or absence of a base. -Solvents used in the reaction include, for example, 1,4-dioxa ^, tetrahydrofuran, ethylene glycolone resin methinooleate, tert-butylinolemethinole, etc. Alcohols such as methanol and ethanol, propanol and the like, nitriles such as acetonitrile, acid amides such as N, N-dimethylformamide, sulphoxides such as dimethylsnorreoxide, water, and mixtures thereof. Give up.

'' Bases used in the reaction include sodium metal carbonate, potassium acid, alkaline metal carbonates such as sodium bicarbonate, lyethylamine, disopropylethylamine 1,8-diazabicyclo [54,0デ 7 7 デ が が が が が が が が が が が が が が が が が が が が が が が が が が が がI can do it. — — ~ ^{: The} compound (3 ′ 2) is usually in a proportion of 1 to 5 mol, and the base is usually in a catalytic amount to 10 mol with respect to 1 mol of the compound (21). - The reaction temperature of the reaction is usually in the range of 0 to 120 ° C., and the time between the reactions is usually in the range of 1 to 24 hours. ------------

After the reaction is completed, the reaction mixture is extracted with an organic solvent, and the organic layer is washed with acidic water (eg, dilute hydrochloric acid) as necessary, followed by post-treatment such as drying and concentration. Compound (33) can be isolated. The isolated compound (3-3) can be further purified by chromatography, recrystallization, or the like; Compound (34) can be purified by a method similar to (Steps 11 to 14) of Intermediate Production Method 1, The reaction can be carried out using compound (33): instead of compound (25-). -.—------.. The compound (2b) can be obtained in place of the compound (2 6) by a method similar to the intermediate production method 1 (Steps 1 1 to 5). The compound can be produced by reacting the compound (34). ―-"―.-. —-. — Intermediate production method 4

• ノレジメチルェ一テル、 t e r tーブチル チル^ー ノ -等の ^ テル類 べキサン、 ヘプタン、 ォクタン等の脂肪族炭化水素類 :トルエン、 キシレン等の芳香族炭化水 素類、 -ク口口ベンゼン等の-ハロゲン化炭化水素類、/.酢酸ブチル、 酢酸エヂル等のェ " ステル類、 ァセトニトリル等の二トリル類:、: N, ジメチルホ.ル_ムァ ド等の酸 ' 5 ' アミ ド類、 ジメチルスルホキシド等のス zレポキシド類及び.これちの混合物があげら れる。. - - - ,: - '⁷-- - 二 , .— — .：..ニ： 反応に用いられる塩基としては、 例えば炭酸ナトリウム、 炭酸力リゥム等のアル '力リ金属炭酸塩類、 水素化ナトリウム、水素化力リゥム等の.ァ:ルカ..リ金属水素化物： 類があげられる。

• Non-dimethyl ether, tert-butyl tyl ^ -no-, etc. ^ Ters Aliphatic hydrocarbons such as hexane, heptane, and octane: Aromatic hydrocarbons such as toluene and xylene; -Halogenated hydrocarbons / esters such as butyl acetate, ethyl acetate, etc., nitriles such as acetonitrile: etc .: Acids such as N, dimethyl fluoride_mud, etc. '5' amides, dimethyl sulfoxide Examples of such bases include z-repoxides and mixtures thereof.---,:-' ⁷ --ii,. Alkali metal carbonates such as carbonated lime, sodium hydride, hydrogenated lime, etc.

 10: The compound (36) is usually in a ratio of 1 to -2 mol per 1 mol of the compound (35),

-Normal base :! 22 mol.

 The reaction temperature of the reaction is usually in the range of 0.0 to L00, and the reaction time is usually in the range of θ5 to -.24 hours. ■-

-After the completion of the reaction, the reaction mixture is extracted with an organic solvent, and the organic layer is dried and concentrated. it can. The isolated compound (37) can be further purified by chromatography, crystallization, or the like. .. ... +-· + ·. ■ Step 14-2; "No-.

The compound (39) can be produced by reacting the compound (37) _:: with the compound (38) in the presence of a base. , ': ..:.,-The reaction is carried out in the presence or absence of a solvent in Byone. --.

 Examples of the solvent used in the reaction include tetrahydrofuran, ethers such as ethyleneglycol mono-dimethyl ether and tex-butyl methyl ether; tonnolee; /, aromatic hydrocarbons such as 25-xylene; : Halogenated hydrocarbons such as benzene, acid amides such as N, N dimethylformamide, sulfoxides such as dimethyl sulfoxide, and mixtures thereof. :...

The base used in the reaction includes, for example, hydrogen hydride: sodium hydride, sodium hydride and the like.Alkali metal hydride, sodium methoxide, sodium ethoxide, potassium-30 tert-butoxide, etc. Al power. Li metal al-cochidide and the like are mentioned _{: δ} ;,: .. '.

 Compound-. (3.8) is usually in a proportion of 1 mol to excess amount per 1 mol of compound (37), and the base is usually :! ~ 5 moles. -.: No ".-.

-The reaction temperature of the reaction is usually 20 ~ :! : Θ-: within the range of 0 ° C _,: Normal during reaction. ~ 24 hours range. ,; ',: ― ”.:--..:.': · ... '-

35 After the completion of the reaction, the reaction mixture is acidified by adding an acid such as dilute hydrochloric acid, and then subjected to a post-treatment operation such as extraction with an organic solvent 1, drying and concentration of the organic layer. Compound: (39- Can be isolated. The singular -compound- (3 :: 9)-can be further refined by...---------------------------- Step 14— 3-■ —.-:---. —::-. · ■: Compound (40) is composed of compound (3-9) and hydroxyreamine or its folate. It can be produced by reacting with sulfuric acid and other salts. — One

 The reaction is usually performed in the presence of a solvent, in the presence or absence of a base. ------. Examples of the solvent used in the reaction are-, for example, aromatic hydrocarbons such as tosolene, xylene: lene, and acid amides such as -N, N-dimethylformamide. And alcohols such as methanol, methanol and ethanol, and mixtures thereof. .- ':.-:-.-;-.,-'-

Bases used in the reaction include, for example, alkali metal acetates such as sodium acetate and potassium acetate, potassium carbonate, sodium carbonate, sodium hydrogen carbonate and the like. Alkoxides such as sodium methoxide, sodium methoxide, potassium te-rt-butoxide and the like. --^

 Compound (39) per mole of -H: '-Mouth is a salt of silamine or liquor.-Usually in a ratio of 1 to-mole, and a base is a catalyst in a catalytic amount of about 3 moles. ■-;; '-

The reaction temperature of the reaction is usually in the range of 20 to 2.100 ° C, and the reaction time is usually in the range of 0.5 to 24 hours. -..

 After completion of the reaction, the compound (40) can be isolated by concentrating the reaction mixture and performing post-treatment operations such as filtration. The isolated compound--(40) 1 can be further purified by chromatography, recrystallization and the like. -· '..:: ":: ..:-,-

(Intermediate production method 5)

[In the formula, βη represents a benzyl group, L represents a chlorine atom or a bromine atom, and Ri, .R 2, R ⁸ , and XY ¹ have the same meanings as described above. : — Step 15 1 to 1.5— 3-— One compound (46) is prepared in place of compound (36) according to Steps 141 to 14-3 of Intermediate Production Method 4. 42) can manufacturing child by reacting with the _n - - - step 15 4: - - - - - - compound (47) compound ^:: (46) and a palladium on carbon and hydrogen It can be produced by reacting in the presence. -.--The reaction is usually performed in the presence of a solvent. --Examples of the solvent used in the reaction include alcohols such as methanol and ethanol, ethers such as tedrohydrofuran, esters such as ethyl acetate, and aromatic hydrocarbons such as toluene. ,-'Mixtures of water and dirt. One-one -The ratio of palladium carbon is usually 0, 0.001 to 0.1 monole per mole of compound (4.6). The reaction temperature of the reaction is usually in the range of 20 to 100 ° C, and the reaction time is usually in the range of 1 to '24 hours. -Knee. After completion of the reaction, compound (47) is isolated by post-treatment such as adding an organic solvent to the reaction mixture as necessary, filtering and concentrating the filtrate under reduced pressure. The isolated compound (.47) can be further purified by chromatography, recrystallization, etc.: :: "-—Step 15-5.". -.

 Compound (48) can be produced by reacting the compound (47) in place of the compound (3) by the-'method according to the production method 3. -":--:

(Intermediate manufacturing method 6) · — ■---.-:-'■ ·-:

[In the formula, R ¹¹ and R ¹² each represent a methyl group or an ethyl group, and R ³ and R ⁶ represent the same meaning as described above. ]

— Step 161-1 — Compound (51) can be produced by reacting compound (49-) with compound (50) in the presence of sodium metal. -The reaction is carried out in the presence or absence of a solvent. Solvents used in the reaction include, for example, ethers such as 1,4-dioxane, tetra-t-drofuran, ethylene glycolone resin methinolate ether, tert-butynolemethinolate ether, and the like. Aliphatic hydrocarbons such as xane, heptane and octane; and aromatic hydrocarbons such as z and mixtures thereof. ..:.--·

 -. 1 mole of compound (49-) is usually 1 to 2 moles of metal sodium, and-Compound (50) is usually 2 moles to an excess amount, and is undereating. -The reaction temperature of the reaction is usually in the range of 100 to 150, and the "reaction time" is usually in the range of 1 to 24 hours. — After completion of the reaction, the reaction mixture is acidified by adding an acid such as aqueous acetic acid, and then the organic solvent is removed. The organic layer is dried and concentrated. The compound (5-_ .1): can be isolated by carrying out the post-treatment operation of the compound.—The isolated compound (5.1) can be isolated by Kuguchi-Matog. According to et al: Can be refined roughly.

 Step: Τ6-2 "--Compound (53) can be produced by reacting compound (51) with compound (5.2).

• The reaction is usually performed in the presence of a solvent. . '-One ...-

 Examples of the solvent used for the reaction include: 1,4-dioxane, tertiary hydrofuran, ethylene glycol dimethinol ether, terbutyl methyl ether, and the like; hexane, heptane, octa X _______________________________________________ include aliphatic hydrocarbons such as _, acid amides such as dimethylformamide, acid anhydrides such as acetic anhydride, and mixtures of these.

The ratio of -J ligated product (5 '2') · is usually Γ to-Ϊ "mono"-per mole of -did product (51). The reaction temperature is usually in the range of 50 to 150. The reaction time is usually in the range of 1 '^ 24 hours.

 After completion of the reaction, the compound is subjected to a post-treatment operation such as concentration of the reaction mixture to obtain the compound.

(53) can be isolated. The isolated compound- '(53) can be purified by chromatography, recrystallization or the like. -Process 1.6-3

 Compound (55) can be produced by reacting compound (53)-with compound 5A) or a salt thereof such as hydrochloride, sulfate and the like.

 The reaction is usually carried out in the presence of a solvent, in the presence or absence of a base.

Examples of the solvent used in the reaction include alcohols such as methanol and ethanol, and aromatic hydrocarbons such as toluene, xylene, and the like: .-N, .N-dimethyles: phor. Acid amides such as mead, water, and mixtures thereof. '-:.--■-■■ 7 ·: As a base used in the reaction, for example, carbon dioxide such as hydrogen carbonate, sodium carbonate: aluminum, carbonated lime, etc. Salts, sodium hydroxide; hydroxides such as hydroxides, hydroxides, sodium-rivum menotoxide, sodium hydroxide, gallium te rt- -Metal alkoxides such as butoxide あ げ '.' · '^. ::: :::. ^: Ι ^: ■■■

-The compound (.54) is usually in a ratio of 1 to 3 mol per mol of the compound (53). 1. When a base is used, the amount is usually in the range of -0.1 to mono. The reaction temperature of the reaction is usually in the range of Q to 150 ° C. The reaction time is usually il to 2 -4.

5 hours range. --—

 After completion of the reaction, the compound (¾-5) ′: can be isolated, for example, by performing a post-treatment operation by the following method. -· .-—: 'Yes.-.--,:.

-(i) Reaction ^; a method of adding an organic solvent to the mixture, if necessary, and concentrating the mixture. -;

 (ii) If necessary, an organic solvent is added to the reaction mixture, the mixture is filtered, and the filtrate is concentrated. "--.

 The isolated compound 55) is further purified by chromatography, recrystallization, etc.

-You can do it. - - - ^: ..- ■ - '.' Two .. -:.. Process 16 4 - ^v two: -.. - - - '-:

15 Compound (56) can be produced by reacting compound (55) with water in the presence of a base. --The reaction is usually carried out with water and an organic solvent.

Fi ^{1 in the} presence. --.: ---. ..:-..--\ '· --..- Examples of organic solvents used in the reaction include methanol, ethanol, and the like. ―Ruco :: -―, teretrahydrofuran, 1,4-digiosan, etc., and mixtures thereof. "■"-'

 -Examples of the base used in the reaction include, but are not limited to, hydroxyl, potassium hydroxide, aluminum hydroxide, and metal hydroxides such as sodium hydroxide. .

 The amount of the base used in the reaction is usually 1-Ό.mol,

-The ratio of :-..:

The reaction temperature of the reaction is usually in the range of 0 to 120 ° C., and the reaction time is in the range of 0.5 · 4 hours. , · — _. '

• After completion of the reaction, the reaction mixture is acidified by adding an acid such as hydrochloric acid, and then extracted with an organic solvent, followed by a post-treatment operation such as drying and concentrating the organic layer to obtain the compound (5: . isolation, can be isolated compound to the; - click (5-_6-.) _-:.. Roma on the graph I over recrystallization koto: can be further purified by 30 ',.. -..:: ':. Step 16-5:-· '11-.'--; 2.:::: ^^ Compound (57) is converted to compound (.56) chlorinating agent- React with ':: r _: produce:-can---2: 1-2

35 The reaction is carried out in the presence or absence of a solvent.

The solvent and "^ Te is that Chi used in the reaction: for example, is milled by ^wet:. Emissions, key register, etc. aromatic hydrocarbons Halogenated hydrocarbons such as benzene and black benzene, and mixtures thereof. : Examples of the chlorinating agent used in the reaction include, for example, thionyl chloride, oxychloride, and lean. .... - - - -: -; - Compound (111) was ¾ · 1 mole ratio chlorinating agent is usually 1 mole to excess: the reaction temperature of _¾ the reaction is usually one 20 Reaction time is usually instantaneous in the range of -1 CO ° C

~ 24 hours range. '-::--.. +:.-After completion of the reaction, compound (57) can be isolated by performing post-treatment operations such as concentration of the reaction mixture. The isolated compound (57)-is obtained by distillation or the like;

-Can be refined. : '-:-:..-=

—Process 16— 6

 Compound (58) can be produced by reacting compound (.57). -'

 The reaction is performed in the presence or absence of a solvent. '

Solvents used for the reaction include 1,4--1, oxane, tetrahydrofuran, -furan,-.: ^ thylene glycolone-dimethinoleether, -1 _e , rt ethers such as butynolemethinoleether, Aliphatic hydrocarbons such as hexane, heptane, and octane; hydrogenated hydrocarbons such as chloroplone; esters such as butyl acetate and ethyl acetate; Acid amides such as N, N-dimethylformamide Byone; sulfoxides such as dimethylesnolefoxyside; water; and mixtures thereof. _

'Examples of the ammonia used in the reaction include ammonia gas and aqueous ammonia. ...-[-.: ■ '. ..;.-:.-:::-. The amount of ammo is usually 0.1 mol to excess per 1 mol of compound (5-7). '-The reaction temperature of the reaction is usually in the range of −20 to 100 ° C., and the reaction time is usually in the range of instantaneous to 24 hours. After completion of the reaction, compound (58) can be isolated by performing post-treatment operations such as concentration of the reaction mixture. The isolated compound (5: .8-) can be further purified by chromatographic chromatography. — 7:. —. —:-Compound (59) can be produced by reacting compound (58) with bromine in the presence of a base.

-The reaction is usually carried out in the presence of water and an organic solvent. · · ·--· · ·:

-Examples of the organic solvent used in the reaction include: U4-dioxane, tetrahydrofuran, ethylene glycolone resin methinolle tenoré, -tert buty-human lemethinolete te; ethers such as k., Hexane, heptane , Odatan and other aliphatic hydrocarbons, Torr: · ■ And aromatic hydrocarbons such as benzene, and benzene and the like, and mixtures thereof. — · '...' — ',. .... Two - is Te base capital 'Les used in the ^reaction;: such as lithium hydroxide, hydroxide force I © beam, alkali metal hydroxides, sodium water oxidation, and the like. -. '-Compound (58) 1-Monole, base is usually at a ratio of 1: 1.0. Mol, and bromine is usually at a ratio of 1-2 mol. -'.-: ∑,-■-..:. ..; ■-―

-The reaction temperature of the reaction is usually in the range of 12 QO ° G: the reaction time is usually instantaneous _ to 24 hours. : - 'single' _-:: 1 - '",..':.. · -"; -: -: ■.

-After completion of the reaction, compound (59) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (59) · can be further purified by chromatography, recrystallization, or the like.

(Intermediate production method 7)

,-(63)-—.. _: “— One-, [wherein L ² represents a chlorine, bromine or iodine atom, and R ³ , R ⁶ and

R ¹⁰ has the same meaning as in the above '. ]::.-:---Step 17-1 and Step 17-7-2

 -Compound (39) can be produced in the same manner as in Intermediate Production Method 4. ― · ,:-Process 1 7― 3. -... I--.: · ': -—,:.,--.

— Compound (63) is -compound (-3: -9 :-). -And—compound: 5 -4) or its -salt (eg, 1, salt: Acid salt, acetate) to produce: … ·. ... • The reaction is usually performed in the presence of a solvent: in the presence or absence of a base. ·--Examples of the solvent used in the reaction include:-aromatic hydrocarbons such as dolene and xinine; N, N-dimethylformamid. K and the like; -Tall and other 5--5 'alcohols and mixtures thereof. .. ~ ~: .no:--;: ~:--The bases used in the reaction are: eg-acetic acid acetate-trim:, such as acetic acid rim: ~-potassium metal acetates Alkali metal carbonates such as sodium bicarbonate, sodium carbonate, sodium carbonate, sodium carbonate, sodium carbonate, sodium carbonate, sodium carbonate Roh Jobs: shea Ηί class is Abachireru _{έ -'.- ~: ^ '- 10} - relative to the compound (39) ί mol,: compound (· 5'4) or a salt of each usually 1～- The ratio is 3 moles, and the base is a catalyst amount to 3 moles. ----,-.:--The reaction temperature of the reaction is usually in the range of -20 to 10 ° C, and the reaction time is usually in the range of 5 to 24 hours. --::-.--After completion of the reaction, 15 compounds (63-) can be isolated by concentrating the reaction mixture and performing post-treatment operations such as filtration. The simple ^ a ^^ product (6-3)-can also be roughly purified by chromatography, recrystallization, or the like. --? : ':

20. [In the formula, R ¹¹ represents a C 1 -C 4 alkyl group, and R ³ and R ⁶ have the same meaning as described above. Step 18-1-· _Π--1.: · ;. —: 1.--:-Compound (6.6 · 6_) is a compound-(64-) azide agent-. In other words, it is possible to manufacture by making .-:.--

The reaction is usually performed in the presence of a solvent. -.-+ One

-25--Compound- Γ65) can also be used in combination with a solvent '-; Compound (; 6.5) Examples include methanol, ethanol propylene, butyl alcohol, .. ter .-: t: monobutyl alcohol. ..-■ ": to: ■----The azide used in the reaction is, for example: diphenyl: phosphoryl lua" zide, dinatrium toxide and the like. .--■,.:--R

--The reaction temperature of the reaction is usually in the range of 0 to 1.1 ° C, and the reaction time is in the range of 2 hours. -'-:: — ■ .— ·:' ·.--:: _..- ·-·:.;. · .: · ·:-: After the reaction is completed, concentrate the anti- ^ mixture. In the post-treatment operation, the compound :. ("6.") can be isolated. ·-■-----,--.-:-Step 18-2- ^: no:. 'One two--.:: ー: No

-Compound (63) can be produced by reacting compound (6-6) with water in the presence of an acid. , —: — —-.... '.-The reaction is usually carried out in the presence of water and organic acids. '.-----

-Examples of the organic acids used in the reaction include trifluoroacetic acid; acetic acid; propionic acid; and mixtures thereof. :: .—;:-:-'.-—. ..—;' ":-; ■:: The reaction temperature of the reaction is usually in the range of 40 to 120 ° C. Normally 0 5: Up to 24 hours-----.

 (67) (63) (68)

[In the formula, R ¹ R ² , R ³ , R ⁷ and L ² — have the same meanings as described above. Γ-.--. ■: = The reaction is usually performed in the presence of a solvent. -■ ”— '— · ·: ..:':

Solvents used in the reaction include, for example, -1,4-dioxane, tetotehydrofuran, ethyl glycol dimethyl: ruel: t. "Ert-butyl methyl ether, etc. Aliphatic hydrocarbons such as ethers, hexane, heptane and octane; aromatic hydrocarbons such as toluene and keylene; Examples include hydrogens, esters such as ethyl acetate and butyl acetate, nitriles such as a-r.-tolyl, sulfites such as methifif: sulfoxide, and mixtures thereof. .--:

 -Examples of the base used in the reaction include: carbonates such as sodium carbonate -V.Pharma and carbonic acid-force-ream, etc., dotylamine-; disop-opene-noreth.ethylamine, 1,8-diaza: bishikuro [ 5, 4, 0] Pendek 7-d--1,-, 5:-diazabishi; b, [4, --3, .1 0] no Nitrogen-containing aromatic compounds such as tertiary amines and phenylamine; _, 4 dimethylaminopyridine. -'Compound (.6: 3) is usually 0.52 mol, and base is usually 1 to 10 mol, per 1 mol of compound (67). -.-;;: .-:--.

-The reaction temperature of the reaction is usually in the range of 0 to -5O 0 C, and the reaction time is usually in the range of 0.1 to 24 hours. , Two ',,......

: After completion of the reaction, the reaction mixture is spiked with an organic solvent, and required.: Add water: Add water. Concentrate:-Add water, extract with organic solvent, dry,-: _ Concentrate. By performing the reward processing operation, the compound (6.8) can be isolated. : Isolated foods 6.) can be further purified by bears, small grains, recrystallization, etc. ---Next, four specific examples of the compound of the present invention are shown below.

 Ad compound represented by formula (A-1):

[Wherein RR ² and RR ⁴ are the substituents described in Table 1 ′. ]

Amide compound represented by formula (A-2)--- OCH

 (A-2)

-[Wherein RR ² and R ³ \ R ⁴ are the substituents described in Table 1. -An amide compound represented by the formula (A-3).

基である。〕 式 (A— 5) で示されるアミ ド化合物.. - ： ： . - ；: 一 -

[Wherein RR ² , R ³ , and R ⁴ are the substituents shown in Table 1. An amide compound represented by the formula (A-4)...,-:-'.

Group. An amide compound represented by the formula (A-5) ..-::.

Wherein the ^{R- -; R 2, __ =} R- 3, R is a substituent described in Table 1 - is. ] Amide compound represented by the formula (A-6)

[R ¹ R ² , R ³ and R ⁴ in the formula are —substituents described in Table 1] Amide compound represented by the formula (Α——7): 11-, '-

[Wherein RR ² , R ³ , and R are substituents described in Table 1. ];-

(表 1の続き)

(Continuation of Table 1)

(表 1の続き）

(Continuation of Table 1)

(表 1の続き）

(Continuation of Table 1)

(Continuation of Table 1)

式 （B— 1) で示されるアミ ド化合物 である。〕

Amide compound represented by formula (B-1) It is. ]

 -

[R ¹ R ² , R ³ and R ⁵ in the formula are the substituents shown in Table 2. An amide compound represented by the formula (B-3) ^:

Group. ]

[Wherein R ¹ R ² , R ³ , and —R ⁵ are the substituents described in Table 2. ] Amide compound represented by formula (B-5)

[Wherein RR ² and RR ⁵ are substituents described in Table 2. The amide compound represented by the formula (B-6Γ)

[In the formulas, R ¹ R ² , R ³ , and R ⁵ are the substituents described in Table 2. .) Amide compound represented by formula (B-7) ·· -----'-·

(表 2の続き） [Wherein RR ² and R ³ \ R ⁵ are substituents shown in Table 2. ]

(Continuation of Table 2)

〔表 2の続き）

[Continuation of Table 2]

本発明化合物が防除効力を有する植物病害としては、 例えば藻菌類によ 植物病 害があげられ、 具体的には例えば次の病害があげられる。 ' '' ' - " 蔬菜類、 ダイ コンのベと病 （Peronospora -brassicae)-、 ·ホ.ヴレンソ "ゥのべと病 (Peronospora spinaciae)、 タノ ^ fのへと病 (Peronospor.a

'ノ リ ¾|の ベと (Pseudoperonospora cuDensis)、 フ r "ゥのべと炳 (Plasmopara yiticola)、. リ ンゴ、 イチゴ、 ャクヨウニンジンの疫病 （Phytophthora cactorum)、 トマト、 キ ユウジの灰色疫病 (Phytophora capsici)、 ノヽ⁰イナップノレの疫病 (Phytophthora cinnamomi) , シャガイモ、 卜マ 卜の疫病 (Phytophthora inf estans)、 'ダパ 、 'ソ ラマメ、 ネキの投炳 (Phytophthora nicotianae var. nicoti裏 e)、 ゥ，レン:ソゥ の立枯病 (Pythium sp. ) , キュゥリ-田 AL枯病 (Pythium aphanidermatura) _Λ コムギ '掲色雪腐病（Pythium sp. )、タバコ苗立枯病 (Pythium debaryanum)、ダイズの Pythium rot (Pythium aphanidermatum, P. debaryanum, P. irregulare, P. mvr iotylum , P. ultimum)₀ ·--■■' .. 本発明化合物を有効成分として含有する殺菌剤組成物は、.本発明化合物と:担体 (carrier) とを含有する。 担体は本発明化合物に対して不活性であり— Γ¾殺菌剤 糸且成物の施用形態等に応じて適宜選択される。 該殺菌剤組成物は、 必要に応じて界 面活性剤等の製剤用補助剤を更に含有していてもよい。 該殺菌剤組成物は、 乳剤、 —水和剤、 顆粒水和剤、 フロアブル剤、.粉剤、 -粒剤等の製剤形態を含む。 該殺菌剤組 成物は、 本発明化合物を通常 0 . 1〜9 0重量％含有する。 ：. ' - " 製剤化の際に用いられる固体担体としては、 例えばカオリンクレー、 アツタパル ジャィ トクレー、ベントナイ ト、モンモリロナイ ト、酸性白土、パイロフィライ ト、- 5 タルク、 珪藻土、 方解石等の鉱物、 トウモ '口コシ穂軸粉、 クルミ殻粉等の天然有機- -

Examples of the plant disease in which the compound of the present invention has a controlling effect include plant diseases caused by algae, and specific examples include the following diseases. ''''-"Vegetables, Radish Downy Mildew (Peronospora -brassicae)-, Ho. Vrenzo" ゥ Downy Mildew (Peronospora spinaciae), Tano ^ f Downy Mildew

Pseudoperonospora cuDensis, Pseudoperonospora cuDensis, Plasmopara yiticola, Phytophthora cactorum, Phytophthora cactorum, Tomato and Phytophora capsici ), Nono ⁰ Inappunore of late blight (Phytophthora cinnamomi), Shagaimo, Bokuma Bok of late blight (Phytophthora inf estans), 'da path,' the Soviet Union Ramame, To炳of Neki (Phytophthora nicotianae var. nicoti back e), ©, Ren : Soybean wilt (Pythium sp.), Cucumber field AL wilt (Pythium aphanidermatura) _Λ Wheat 'Snow color rot (Pythium sp.), Tobacco seedling wilt (Pythium debaryanum), Pythium rot of soybean (Pythium aphanidermatum, P. debaryanum, P. irregulare, P. mvr iotylum, P. ultimum) ₀ : A carrier, which is inert to the compound of the present invention. Γ¾ Disinfectant The disinfectant composition is appropriately selected depending on the application form of the yarn and the like, etc. The disinfectant composition may further contain a formulation auxiliary such as a surfactant, if necessary. The fungicide composition comprises an emulsion, -Includes formulation forms such as wettable powders, wettable powders, flowables, powders, and -granules. The fungicide composition usually contains 0.1 to 90% by weight of the compound of the present invention. : '-"Examples of solid carriers used in the formulation include kaolin clay, attapar jacto clay, bentonite, montmorillonite, acid clay, pyrophyllite, -5 talc, diatomaceous earth, calcite and other minerals, and corn. Natural organics such as mouth cob flour and walnut shell flour--

-Synthetic organic substances such as urea, calcium carbonate, salts such as ammonium sulfate, synthetic hydrous powders and granular substances made of synthetic inorganic substances such as silicon oxide, etc., and the liquid carrier is, for example, xylene. , Alkylbenzene, methyl naphthalene, etc., and aromatic alcohols such as 2-propanol, ethylesiglycol 'chol, propylene glycol', and cello 10 noreb, acetone, syrup, kebexanone and isophorone. Cosmetics,-Vegetable oils such as soybean oil and cottonseed oil, petroleum-based aliphatic hydrocarbons, esters methylsnorreoxide, acetonitrile, and 7J. „Surfactants include, for example, alkyl sulfate earth salts, alkylarylsulfonates, dialkylsulfosuccinates, 'polyethylenealkyla'arylates 15 tellurates, ligninsulfonates, Anionic interfaces such as naphthalene sulfonate formaldehyde- aldehyde polycondensate. Nonionic agents such as surfactants and polyoxyethylene alkyl acrylates, polyoxyethylene annalequinole polyoxypropylene block copolymers, sorbitan fatty acid esters, etc. Surfactants. '—-

"."-Other pharmaceutical adjuvants include, for example, polyvinyl alcohol, Polyviel i

20 Water-soluble polymers such as 1-lidone, gum arabic, alginic acid and its salts, polysaccharides such as CMC (forced methoxymethylcellulose), xanthan gum, and inorganic substances such as anolemminium magnesium silicate and alumina sol , Preservatives, colorants, stabilizers such as PA-P (acidic acid mouth pill) and BHT. :

 -The fungicide composition of the present invention is used to protect S from plant diseases by, for example, treating plants, and growing on the soil by treating the soil. -Used to protect plants from plant diseases. ''.

When the fungicide composition of the present invention is used by applying foliar treatment to plants or by applying it to soil, the treatment amount is a plant to be controlled. type, § raw about control target disease, formulation form, treatment period, but may be varied depending meteorological 30 conditions, OOOO m ² per the present invention compounds - generally 1 as an object

5500 g, preferably 5 ^ 100 g. '' ■

-Emulsions, wettable powders, flowables, etc. are usually processed by diluting with water and spraying. In this case, the concentration of the compound of the present invention is usually 0.0013 to 13% by weight, preferably Ό. Powders, granules, etc. are usually treated without dilution. _

Further, the fungicide composition of the present invention can be used in a treatment method such as seed disinfection. So For example, the method of the present invention is to immerse plant seeds in the fungicidal composition of the present invention prepared so that the concentration of the compound of the present invention is-1 to 1: 100 pPm. Spraying or spraying the seeds of the present invention on plant seeds ^: • Spraying or smearing the fungicide composition of the present invention with a compound concentration of 1 to 100-O ppm A method for dressing the fungicide composition of the present invention is described below. The method for controlling plant diseases of the present invention generally comprises treating an effective amount of the fungicidal composition of the present invention with a plant in which the occurrence of a disease is predicted or a soil in which the plant grows, and Alternatively, if the disease has been confirmed, the plant will grow if it is found: treating it with soil.

. —Ϋ is done. ·-,.

—--The fungicide composition of the present invention is generally used for controlling plant diseases for agricultural and horticultural use; that is, for controlling plant diseases such as upland fields, 'paddy fields: 臬 trees: 10- orchards, tea fields, pastures, lawns, etc. Used as a plant disease control agent. The fungicidal composition of the present invention may be used for other plant disease controlling agents, insecticides, acaricides, nematicides,

· Can also be used with herbicides, plant growth regulators and Ζ or fertilizers. · ':: two.

"The active ingredients of such plant disease control agents are:

15 Nam, Zikuguchi Fluanide, Josetyl-A1, _Cyclic imide derivatives (capyad, capitahonore, phonorepet, etc.), dithiocarbamate derivatives (manneb, mancozebu, thiram, ziram, zineb, prozeneb) Etc.), inorganic copper salts are organic copper derivatives (-basic copper sulfate, basic copper chloride, copper hydroxide, oxine copper, etc.), and a: n-alanine derivatives (me. , Cypro: furan, benalaxinole,: oxazine, 20xyl, etc.), stoline bil-lin _ compounds (cresoki, methethyl-,.口 ビ ン ス · ピ ピ ピ ピ ジ ジ ジ ジ ジ ジ ビ ン ビ ン ビ ン 口 ビ ンTwo -... Pirimu etc.), phenylene Rubiroru derivative (full We ^ Pikuro alkenyl, Furujiokisoniru etc.), imide derivatives (Puroshimi Don, Eve dione ^ link port ethylbenzthiazoline etc.), Benzuimida -.

25. Zole derivatives (carbendazim, besomyl, thiabendazole, thiophane small methyl, etc.), amine derivatives (fenpropimoneolef, small lidemorph, -phen: npropidine, ----... Spiroxamine), azole Derivative '· (Pico Picona-Zole; Tri 7: Dimeno-No- &, Ipe-Chloraz, Penconazonole, Teb' 33.Nazo-Nore, '. ,, Bromconazonore, Epoxyconazonore, Difenounazonore, Ship mouth co-nazonore.,-

30 Methoconazole, Trinole mizonole,-La-Conazo: Le-,-Mike mouth butanyl, Fenbuconazole, Hexaconazole-, Funoleki ^.

-J-bitertanol, imazalil, furth .. liarol, etc.), simoki-sa-nisole, di; ^ Noreb: -Cyazofuamide, Zoxamide, Taboxam,. _: Nico-bihue, Fuenhexamid,-

35 Quinoxifene, dietofencanoleb and acibenzolar S-methyl. Hereinafter, the present invention will be described in more detail with reference to Production Examples, Production Examples, Test Examples, and the like, but the present invention is not limited to these Examples. First, production examples of the compound of the present invention will be described. :--Production example 1— 1 ·-.-·-■ '

 5 Amino 4- (3,4-di-methoxyphenyl) -isoxazole -0, 37 g and -triethylamine Ό-. 50 g- is dissolved in tetrahydrofuran 1 -Om 1 and 0.2- (4-chlorophenyl) -acetic acid chloride (0.4.4-Q g) was added dropwise, and the mixture was stirred at room temperature for 3 hours, and then ethyl acetate was added to the reaction mixture. The filtrate was concentrated under reduced pressure, and the residue was subjected to silica gel chromatography (developing solvent: ^ hexane ethyl acetate = 1/1)-to give N {. (3,4-dimension). Doxyf: nil) isoxazole-5yl} —2- (· 2propieroxy) 2- (4-chloroacetate: phenyl) acetamide (hereinafter referred to as product—1-1) .0.049 g was obtained. Was.

 Product 1— 1-■ r

— NMR (CDC 13, TS) δ (ρ ρ m): 2-. 5 6 (1 Η, -t, -J = 2 _r . · Η ζ 3.7 1 (3 Η,-s):,: '3 .-— 8 8 (3 Η, s) -4. 1 2-(-1 Η, -ddd:-J = 2.4 Hz, 15.8 Hz 4.38- (Ι Η,-d d- _r J = 2.4 Hz, 1-5.

 .7 7 -.6. .80 (3H m), 7. .22-7.s), -87 5 (tH, -s) ―

Production Example 2 1— ^ ■ · ^; ---------■ Toluene 1 50 m 1 in 4 methylsenyldalioxylic acid 10 .. _0 g and thionyl chloride 7.2 m 1 and N, N-dimethylformamide (0: 0.2 g) was added, and the mixture was stirred at 80 ° C for 1 hour :. Thereafter, the reaction mixture was allowed to cool to around room temperature, and concentrated under reduced pressure to obtain 12.1 g of f crude 4 · -methylphenyldaloxyl chloride. ··· Two:-■: .-. Tetrahydrofuran 50 ml: Mix product 2.1-g of 6-a with Tritylamine 2-m1 and add this mixture At 0.5 ° C., 1.8 g of the above crude 4-methylthiol-g: lyochloride-silicic acid chloride was added, and the mixture was stirred at room temperature for 2 hours. -After that, water was added to the reaction mixture-: concentrated, concentrated under reduced pressure, and extracted with chloroform & times. .Organic ;! The residue was subjected to silica gel chromatography to obtain 1.4 g of a product having the following physical properties (hereinafter, referred to as _-product 21). -----...

Product 2—1—One- ^-1 H-NMR- (CDC 13, TMS) δ. (P pm) .2. -45. (3 H-, ^1- s), 3. -9 "4- (3 H-, · s), 3.97- (3H;: s); 3.9.-9 (3H, s) ,. 7.00-718 (-3H, m), 7.-31 (2H; d, J 8 H), — 8, 26: (-1:,-1 s), 8 — 3 6- (2H, d, J = 8 Hz), .9.16 (1 H, brs) "

 -

Production Example 2—2...-:……-'1.:-Product 1-1 g of 2-1 is mixed with Etano-1 / Leni 20 ml:-, where 0 to 5 Then, 33 mg of sodium 7-borohydride was added thereto; and the mixture was stirred at room temperature for 5 hours. Thereafter, the reaction mixture was concentrated under reduced pressure, water was added, and the mixture was extracted three times with a black hole. . The organic layer was dried, vacuum 'and lower concentrated product of the physical properties of the following (-. Or less, the product 2 2 referred) 1 L_g give the _ό product 2 2 - - -:: - -. .. '- · ■ - - .:.

— NMR (CDC 13, TMS) δ (ρ ρ m "): 2..3.6 (3 Η, s),-3..3: 1 H, d), 3.88 (6H, s), 3. 92 (3 H, s), 5. 2 (1—H, d)-, · 6. · 86—7.21 (5-H, m),. 33 (2H, d, J = 8 Hz) v'8. 06 (1H, s-), 8.2 (1H, brs)- _: ----

 Production example 2-3-2-. F: no. '■ ,,:

-'20 g of product 2-1 is mixed with 5 ml of methanol, and-0-methylene: droxy-, 57 mg of luminamine hydrochloride and pyridine 0 · G5 1 ml are added. Stir for hours. Thereafter, the reaction mixture was concentrated under reduced pressure - to Γ residue was purified by thin-layer chromatography - preparative I one minute -:. Hatred made to the product of the following physical properties (hereinafter: the product - _2-3: and 0.0-, l, 4 -.- g. ^ Narubutsu 2 3 .. ::. -,:, - -, Two:;:.... " H one _{NM-R (CDC 1 3,} - TM S) δ (ppm): -2". 3 "7 (3H, s)-, .3,.,: 8-7-. (: 3H, s), 3.91 (3H, s), 3.95 (3H, ' _S. ), 4.Θ4 (-3H; 's), 2.6.92 (1H, d, J 8.4 Hz), 7.09 (1, H, dd J = 84, 2.

0H z), 7.14 (1 H, d, J = 2 :: QHz), 7.19 (2H, d, J = 8. 4Ή ζ), 7.45 (2Ή, dp =: 8.4 Hz, -8 · 1-5 (ΙΗ, brs) \ 8. "2 3- (1Η, s)

 Production example: 2-4:-", .- ::,.

'Tetrahydrofuran · 20 ml of product 2-' 0-71 g of 2 and triethylamine 0.

Then, 0.21 ml of methanesulfoninol chloride was added dropwise at around 0 ° C .: The mixture was stirred at room temperature for 2 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with 3% hydrochloric acid and water, dried, and concentrated under reduced pressure. To the residue, 3 ml of Λ2-loop: mouth'-pin-1-ol was added, and the mixture was stirred at about −8 ° C .: for 2 hours. Then, the reaction mixture was allowed to cool to near room temperature, water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with water, saturated aqueous sodium bicarbonate solution and saturated saline, then dried, concentrated under reduced pressure, and the residue was subjected to silica gel chromatography to obtain the following physical properties. The product (hereinafter referred to as.;-Product 2—)-0.50 g was obtained: -.. —--Product 2— 4-::.-

_{^{1 H-NMR (CDC 1 3}} , TM S) - δ (ppm):. 2 • 35 (3H, s), 2 4. 8 -2 49 (1 H, m), 3. 89 (3 H, s ), 3 95 "(3 H, s), 3 9

6 (3H, s), 4.01 -4.30 (2-H, m), 514 (1 ¾s), 6 9

 H, m), 8.08 (

2. 4 gとジフエニルホ スホリルアジド.2. 6 g-と h -ェチルアミン 1 0 gとを混合し、. 還流下 6時間攪- 拌した。 反応混合物を減圧下濃縮し； 残渣をシリ力ゲルク口マトダラフイ一に付し- た。 得られた精製物と トリフルォロ酢酸 lm 1と酢酸 3 m 1と水- lm 1とを混合し、 60°Cで 3時間攪拌した。 室温付近まで放.冷した反応混合物に水を加え、二酢酸ェチ ノレで抽出し、 有機層..を飽和炭酸水素-ナトリウム水溶液で洗浄後、 減圧下濃縮した。 - られた残渣と トリェ-チノレア.ミ-ン 0. 50 g-とをテトラヒ ド t？フラン 10m に混 合し、 ここに 2— < 2—プロ-ピオ-ルォキジ） —2— (4 グロ口フエニル） 酉乍酸 塩化物 0. 50 gを加え、 室温で 4時間攪拌した。 その後反応混合物を減圧下 ¾S縮 • し、 残渣をシリカゲルク口マトダラフイ一に付:し、.下記の物性の生成物 （以下、 生 成物 2— 5と記す) 0 43 gを得た。 . ·' " - 生-成物 2— 5 · - -:, - . ' - iH— NMR (CDC 1₃，. TMS) δ (P P— in) ： 1. 46 (9H, s)、 2. 43 (1"H, t , J =2. 4H zゥ.、 3. 8 -4. 00 (7H,—m)、. 4. 08— 4. .1.6 (1-H, m)ゝ 4. 98 ( 1 H, s ) 6. -7: 5— 6 · · 9 & (3 . m)、 7. 1 6 - 7. 30 (4H, m)、 7. 12 ( 1 Η,ν s.)v 7. _95— ( 1Ή，- s：) - .— - ： ' ~ '：" - - " —

2.4 g of diphenylphosphoryl azide, 2.6 g- and 10 g of h-ethylamine were mixed, and the mixture was stirred under reflux for 6 hours. The reaction mixture was concentrated under reduced pressure; the residue was applied to a matting agent. The obtained purified product, trifluoroacetic acid lm1, acetic acid 3 ml, and water-lm1 were mixed and stirred at 60 ° C for 3 hours. Water was added to the cooled reaction mixture, and the mixture was allowed to cool to near room temperature. The mixture was extracted with a paste, and the organic layer was washed with a saturated aqueous solution of sodium hydrogen carbonate and concentrated under reduced pressure. -The obtained residue and 0.55 g of trie-tinolea. The mixture was mixed with 10 m of furan, and 0.50 g of 2- <2-propio-loxodi) -2- (4 glo-mouth phenyl) acid chloride was added thereto, followed by stirring at room temperature for 4 hours. Thereafter, the reaction mixture was subjected to 縮 S reduction under reduced pressure, and the residue was subjected to a silica gel gel. To obtain a product having the following physical properties (hereinafter referred to as product 2-5) 043 g. . · '"- Raw - Narubutsu 2- 5 · - - :, -. ' - iH- NMR (CDC 1 3, TMS.) Δ (PP- in): 1. 46 (9H, s), 2. 43 (1 "H, t, J = 2.4 Hz ゥ., 3.8 -4.00 (7H,-m), .4.08— 4..1.6 (1-H, m) ゝ 4. 98 (1 H, s) 6.-7: 5-6 · 9 & (3.m), 7.16-7.30 (4H, m), 7.12 (1 Η, ν s.) v 7. _95— (1Ή,-s :)-.—-: '~': "--" —

 Production example 2—6 -.-.-.

 0.43 g of the product 2-5 was mixed with dilute hydrochloric acid 1 Om: l, and the mixture was stirred under reflux for 3 hours. Water was added to the reaction mixture that had been allowed to cool to near room temperature, and extracted with tyl acetate. The organic layer was dried and concentrated under reduced pressure, and the residue was subjected to a series of gel chromatography to obtain a product having the following physical properties: 0-iog. -::------Product 2-6 "

1 Contact _{_NMR (CDC 1 3, TMS)} 8 (ppm):. 2. 5 (1 H, t, J - 2. 4Hz), 3. 92 (3H, -s), .3 95 (3H, s - ), 4, 05 — (1H, dd, J = 2.4 Hz, 15.8 Hz), 4.31. (1 H, dd, J = 2.4 Hz 15.

8 Hz), 5.17 (1 H, s), 6.98. (1 H, d '; J = 8.7 Hz), 7.11 (.1 H, s), 7. 11 (1 H,-d J = 8.7 H-z), 7.34-7.38 (4. H, m), 8.21 s), 8: .60 (1 H, .s) .

OCM, Production example 2 7--..-.,:

2- (2-propynyloxy) 2-(:. 4 chlorophenyl) acetic acid 0: 35 g ,: 0.34 g of product Π-6a, 0.33 g of WS C and above. Lysine S ml. Was mixed and stirred at 70 ° C for 3 hours. Thereafter, the mixture was cooled to room temperature, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed three times with 5% hydrochloric acid; -saturated sodium bicarbonate (0.7 k) and saturated brine in that order; dried over magnesium sulfate; and-concentrated under reduced pressure. The residue was subjected to gel force lambda mouth chromatography to obtain 0.21 g of a product ′ having the following physical properties (hereinafter, referred to as product-2-7). One ... —... '·, ―.:. Product 2— 7-:.-:-:--

! H-NMR (CDC 13, TMS) δ- (ρ pm);: (. 3H, s) 2. 47 (1 Η, t, - J = 2 · - - 4 H z), 3. 89, 3 .95 (3H, s), 3. .96 (_3H, s), 4..05 (1H, dd, J = 16.OHz, -2.4Hz), 4, .. 31 (1H, dd, J = 16.OH z,-2.4 Hz), 5.16 (1H, s), 698 CI H,-d, J =-

8.ΌΗz), 713 (1, dd, J = 8..OH z, .6H ζ) 7.17 (1 H, d, J = 1.6 Hz), 7..37 (4H, s), 806 (1H, s), .8.62 (1H, br.s)--"-

 2-(2-propynyloxy)-2 (.4-butane-m-phenyl)-acetic acid 0.2.6 g: g. Product Π-0.27 g of 6a, 'WS: C 0.26 g And 8 ml of pyridine were mixed and stirred at 70 ° C. for 3 hours. Then, the mixture was cooled to room temperature, and ^ was added to the reaction mixture, followed by extraction with acetic acid. The organic layer was washed three times with -5% hydrochloric acid, sequentially with saturated sodium bicarbonate water and saturated salt water, dried over magnesium sulfate, and then concentrated under reduced pressure. The residue was subjected to silica gel chromatography to obtain a product having the following physical properties (hereinafter, referred to as product 2--8 :)-0.25 g. ―

 Product 2-8

^ -NMR (CDG l- ₃ , TMS) δ (ρ ρ m): 2.51 (1 Η, t :, J = 2τ 4H¾), -3.89 (3H, s), .3.9 B, (3H, s); ': 3.96 (3H, s), 4 .. HI 3. (1H, dd, J = 16Hz, 2.4Hz 4.31 (1H, dd) , ■ J = 1- 6 H z , 2. 4H z), 5. Γ 4 (1::. H, s), 6. 97 '(1 H, d, J = 7 9H z), 7.13 (1 H, -dd, J. = T 9 H z, 2. OH z), 7.1.7 (1 H,-d, — J = 2r 0 Hz), 7.3 1 (2H, d, J = 8: -3Hz), 7.-52-(2H, -.d-J = 8.3Hz), 8.06 (1H, .s), 8.6.6 (1H , .b.r.s-)

製造例 3—1 - . ^: . ： 一 生成物 ΠΙ— 3 aの 1. 08 gをエタソール 1: 0 m l:に混合し、 ここに 0 5 °Gで '水素化ホウ素ナトリウム 32mgを加え、 室温で 2時間攪拌した。 反応混合物を減- 圧下濃縮し、 残渣に水を加えた混合物を 0°C.にした。 濾過して得られた固体を減圧 乾燥し、 下記の物性の生成物 （以-下、 生成物 3— 1と記す). 0. 7-5-gを得た。 生成物 3— 1 '

Preparation Example 3-1-. ^: .: One product ΠΙ-3a 1.08 g was mixed with etasol 1: 0 ml: and added with sodium borohydride 32 mg at 0 5 ° G at room temperature. For 2 hours. The reaction mixture was concentrated under reduced pressure, and the mixture obtained by adding water to the residue was brought to 0 ° C. The solid obtained by filtration was dried under reduced pressure to obtain 0.7-5-g of a product having the following physical properties (hereinafter, referred to as product 3-1). Product 3—1 '

^{. 1 H-NMR (CDC 1} 3, TMS) δ (p pm): 2. 36 (. 3 H, - s -), 3. 71 (3H, s), 3. 86 - 3. 88 (7 H , m)-, 5.18 (1H, s), 6.65-6.78 (3-H, m), "7 17. (2-H, 'd, -J-7,, 6Hz) , 7, 34 (2H, d, no J = 7.6 Hz), 7.38 (1 H, s '), just 85': (1¾, s)

"J;-

 Production example 3-2 + ·.:---;:-.

• .92 g of M-3b was mixed with 10 ml of ethanol, and “0 to 5” and 28 mg of sodium borohydride were added, and the mixture was stirred at room temperature for 2 fl. The reaction mixture was vacuum Shimono reduced, the residue mixture was added water ₅ filtered to obtained solid was dried under reduced pressure to 0 ° C, the bottom:.. Symbol of - product properties Ό 93 g of Obtained.ヽ-.:-.-:.--Product 3 2--. ·.:---. '-

-^-NMR (CDC 13, TMS) δ (ρ pm): 2.38 (3Η, s-), 3.36--(1 H, d, J = -3.2 Hz), -3.67 (3H, -s-), 3.79 (3H,:-s)-, 3. .8 9 (.3 H-, "s.-), 5.28 (1 H, .d, J. = — 3-.: 2 H z), .6. .74— 6. .8-4 -(3 -H, -m), 7-: 22 '(2Η, d, J 8 Hz, 7.36 (2 H, d, J. = 8 Hz--7.5.9 (1 H , S), 7 .-- 87 (1 H, s) —-'. -—:.' Production example 3: 3 ·

 0.5-5 g of the product 3-1 and trimethylamine 3 Om l-are mixed with 1 Om 1 of tetrahydrofuran, and 0.13 g of methanesulfonyl chloride is added dropwise at about 0 ° C, and the mixture is added For 30 minutes. Water was added to the reaction mixture; ^, ethyl acetate was extracted. The organic layer was washed twice with water, dried, and concentrated under reduced pressure. The residue was mixed with _2, pron-1-ol 1 · -7 ml and stirred at around 80 ° C for 1 hour. Thereafter; the mixture was allowed to cool to about room temperature, ice was added, and extracted with ethyl acetate. The organic layer was washed successively with water, a saturated aqueous solution of sodium hydrogen carbonate and saturated saline, dried, and concentrated under reduced pressure. The residue was subjected to chromatography to obtain the following physical properties. Product (hereinafter referred to as product 3-3) -2

29 mg were obtained. --'. — .---:-Product 3-3.-: .. · no.,::-

_{^{1 H-NMR (CDC 1 3}} , TMS) δ (pp.m) :: .. 2. 37 (3 H ", s), .2. .5- 1 (1H, t, J = 2. 5Hz) , 3.66 (3 H,-s) ^-3.-78 (3H, s),

3.89 (3 H, s), 4.01—4.33 (2H, m), 5.21 (1 H, s), 6.79-6.85 (3H, m), 7.21 ( 2H, d, J = 8.Hz), 7:33 (2H,

-d, J = 8Hz), 7.59 (1H, s), 8..22. (1H, s.):..-, ■-· '-: "-one: ...

 • Production example 3—4 · .. '::: --- ■-.

-0.6-3 g of product 3-2 and 0.3 and 39 ml of triethylamine are mixed in 10 ml of tetrahydrofuran, and 0.15 ml of methanesulfonyl chloride is added dropwise at about 0 ° C. Stirred at room temperature for 30 minutes. Water was added to the reaction mixture and extracted with acetic acid; The organic layer was washed twice with water, dried, and concentrated under reduced pressure. --The resulting residue was mixed with 2-Pro: Be.1-ol 1.9 ml and stirred at around -80 for about hours. After H, the reaction mixture was allowed to cool to around room temperature, and then water was added. -Organic: The layer was washed successively with water, a saturated aqueous solution of sodium hydrogencarbonate and saturated saline, dried, and concentrated under reduced pressure. The residue was subjected to chromatography to obtain 264 mg of a product having the following physical properties (hereinafter, referred to as "product, 3"). --- Product 3—4

 H-NMR (CDC13, TM-S) δ (ppm): 2 ". 34 (3H, s-), 2_4

 7 (1 H, t, J = 2.4 Hz), 3.-53 (3 H, s), 3.88 (6H, s),

 4.03 -4.28 (2Ή, m), 5..14 (1 H, s), 6.7—6.99 (3

 H, m), 7.-15 (2H, d, J = 8Ήz), 7 · '32 (2Hd, J = 8Hz)-,

 7.39 (1 H, s) ヽ 8.38 (1 H, s)

 Production example 3-5-

'The product in 15m 1 of pyridine 1_δ a 2 ·: 0 g and 2-(4-black mouth fuel).

 1.6 g of 2- (2-propynyloxy) acetic acid and 1.7 g of .1-ethyl-3 "(3-dimethinorea minopropyl) carbodiimide hydrochloride were mixed and stirred at 100 ° C for 2 hours.

 did. Dilute hydrochloric acid was added to the reaction mixture that had been allowed to cool to near room temperature, and extracted with ethyl acetate.

 The organic layer was dried and concentrated. The obtained crystals are washed with Hexane to produce the following physical properties:

'(Hereinafter referred to as / product 3-5) 2.7 g was obtained.

 Product 3-5-^-NMR (CDC13, TMS) δ (ppm): 1.61 (9H, s), 2.51

 (1 H, t, J = 2.4 Hz) ゝ 3.68 (3H., S),-.3.88 (3H, s), 4.

 0 5 (1 H, d d, J = 2.4 H z, 15.8 H z), 4.3.2 (1 H, d d, J

= 2.4Hz, 15.8Hz), 5.-17 ^_ (1H, s), 6.67--6.73 (2Η, m), 6.81 (1H, d, J = 1. 6H z), 7.30 -7. 37 (4H, m),

 7.55 (1 H, s), 7.98 (1 H, s)-.

-Two-

Production Example 3-6 -"1.0 g of product 3-5 is added to a mixture of 6 ml of ethanol and 10 ml of hydrochloric acid (3 mol Z1) and 3 ml of 1,1,4-dioxane 3-and reflux. Water was added to the -reaction mixture and extracted with ethyl acetate.The organic layer was washed with a saturated aqueous solution of sodium hydrogen carbonate, dried and concentrated under reduced pressure.The residue was subjected to silica gel chromatography. The product having the following physical properties (hereinafter referred to as product 3-6) · S lmg was obtained.

_{^{1 H-NMR (CDC 1 3}} TMS) - δ (ppm): 2. 53 (1 so Γ t, J 2 · OH ζ ), 3.- 90 (3 Η, s), 3. "93 (3Η, s), 4. -05, (1Η, dd,-J = 2.0 Hz, 15.8 Hz), 4.32 (1-H, dd, J = 2.0 Hz, 15 ";- 8Hz), 5.20 (1 H, s), -6.87—6.95 (H, m), 7.3.3—7

One

 Production example 3-7-1.

 1.6 g of the product ΠΙ-9 and 1.0 g of triethylamine are dissolved in 2 Om.l of tetrahydrofuran, and then 2- (4-chlorophenyl) 1-2- (2-probutyloxy) ) 1.6 mL of acetic chloride was added, and the mixture was stirred at room temperature for 4 hours. Ethyl acetate was added to the reaction mixture, the mixture was filtered, and the filtrate was concentrated under reduced pressure. The residue was subjected to chromatography, and the product 0.35 g (hereinafter referred to as “-1.5 g of the product having the following physical properties” (hereinafter referred to as “product 3 -.7a”) , And product-3-7 b-, respectively.— Product 3—7a} ——

_{^{1 H-NMR (CDC 1 3}} , TMS) δ (p pm): 2. 49 (1 H, t, J = 2. 4Hz), 3. 74 (3H, s), 3. 88 (6 H, s ), 4.0,9 (1 H, cTd,, J = 2.4 Hz, 15.8 Hz), 4.30 (1 H, dd, J = 2., 4 Hz, 15.8 Hz), 5.15 (1 H, s) 6.47 (1 H, d, J = 8.3 Hz) 6. -7 "7 (1 H, dd, J = 1; 6 Hz, -8.3 Hz) 6 84 (1 H, d, J = 1,-

6 H z) \ 7.31-7. 40 (5H, m), -8.35 (1Ή, s)-Product 3 7 b---.....--. One MR (CDC 1 ₃ , TMS) δ (p pm): 2, 54 (1 H, t, —J = 2. .4 Hz), 3.65 (3H, .s), 3.78 (3H, s), 3. 89 (3H, s), —4—.08 (1H, dd, J = 2.4H ζ ·, 15.8 Hz), 4 · 33 (1H, dd,. J 4H z, 8 H z), 5 2.2 (1 H, s ..), 6 .-: 7 5—6.7 8 (2 ΎΛ,

 H, m-), 7.5 8 (1 ϊί,

 5 · Production example 3— 8. —---,:-.-.-

-After adding 12 g of 4-methylbenzaldehyde and 30 g of bromoform to 50 ml of methanol, a methanol solution of hydroxide hydroxide (28 g of hydroxide hydroxide and 110 ml of methanol) was added. Was added dropwise under ice-cooling. After stirring at room temperature for 1 day, the V-reaction mixture was extracted by adding water and gross mouth form, and the obtained permanent layer was added with hydrochloric acid to make it 10:10 acidic and extracted with kuguchi mouth form-. The organic layer was concentrated under reduced pressure to obtain 1 l g of 2-mexy-2- (4-methylphenyl) acetic acid. .-.....

 • 2-Methoxy-1- (4-methylphenyl) acetic acid

^{- 1 H-NMR (CDC 1} 3, TMS) δ:. (PP m): 2. 3 4 (3 H, s), 3. 3 "9 (3 H, s), 4. 7 4 - ( 1 H, s),-'7 17 (2—H, d,' J = .79 Hz), 15; 7.31 (2 H, d, J. = 7.9 Hz): .:.. — —.-. ..:. —:-2—Metguisy 2—— (4-Methylphenyl): -acetic acid 0, 27 g, product HI—9: -0. . '.-: 35 g, 1-ethyl-3, (3-dimethylaminopropyl) carbodiimide hydrochloride _-(hereinafter referred to as WSC) 0.32 g and pyridine 8 m The mixture was stirred for 6 hours at .1 l. ° C. After cooling to room temperature, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate-20.The organic layer was diluted with 5% hydrochloric acid and saturated aqueous sodium hydrogencarbonate. , -Water and saturated brine, dried over magnesium sulfate and concentrated under reduced pressure.The residue was subjected to silica gel column chromatography, and the product having the following physical properties was obtained. , Product 3-8 a ) —9.1 mg and 80 mg of a product having the following physical properties (hereinafter, referred to as the present compound 3-8 b) was obtained.

-25 ¹ H-NMR (CDC 13, TMS) "¾ (p-.pm): 8.39 (1 H brs) V'7.-38 (1 H, s), 7.3 1- ( 2Ή, d, J = 8. QH), — .7. 1: 4 (.2. H, d, J = 7.8 H z), 6.83 (1-Η, · -d ^ J ^: . ^ 1 ": 7 H z), 6.78 '. (1 H, dd,--J = 8. OH z 1.7 H z), 6 · 7 4 (lH, d J = 8 · ·. 2'H z). ゝ 4 .. .7−2-(1 H, s, 3.87 (3H, s)., 3.86 (3 H, s), 3.64 ′) (3H, s) r 30 3.39 (3Ή, s), 2.33 (3H, s)--,:-. ' Product: 3—- 8 b---------:

_{^ H -NMR CCDC 1 3, TMS} ) - one δ (ppm):. 8 - 1 6 (ΊΉ, br s -) \ 7. into 5 8 (1 H, -s) , 7. 3 2- (2 Ή, d, J = 8; 3 Hz-), 7.20 (2 H, d-1 J = -7.8 Hz), 6.80 to 6.88 (3 H, m) one - 4 · 8 0 - (1 H, s); 3. 8 9 (3 H, s), 3. 7 7- (3 H, s) -, 3. -6 6 (3 H,: s ), 3 .. 40. (3 H, s), 2. 37 (3 H, s) no----: ":---.-

 Production example 3— 9---. '· —.' ―-―. ■ '―

 2-(· 2 -propininole)-2, (.4--buffine fuenoinole)-acetic acid 0 & 4 g Product ΠΙ-0.47 g of 9, WS CO, 4.2. G- The mixture was stirred at 8115 ° C for 5 hours. Thereafter, the reaction mixture was cooled to room temperature, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with 5% hydrochloric acid, 'saturated aqueous sodium bicarbonate; water and saturated saline, dried over magnesium sulfate, and concentrated under reduced pressure. Residue is silica 'gel.

— ^: The product of the following physical properties (hereinafter referred to as “product 3—9— 'a.”)-0.2: 7—g and the product of the following physical properties (hereinafter, the compound of the present invention 3— 9 b) 0.3 1 g was obtained. -.-.,--.:

-Product 3-9 a--■ 1 H-NMR (CDC 13, TMS) δ (ppm): 8 ..- 3.4 (1 H, br-- .s), 7.48 (-2 H , d, J = 8.3 H z) ゝ '3-39 (1 H, s),;: -— .7 ·: 3 3. (2 H,. d, J = 8.5 H z) , 6.8—'2 to 682; (1H, m)., 6.0.7: 2 to 6V 7,6 (2H, m), 5.13 (1H, s), 4 : 3 0. (1 H, .— d d., J .. =. 15.9Ή-ζ 2.4 Hz), 4.10 (1 H, dd, J: 15; .9- H z-, 2, Ή z): —, 3:, 89 9- (3 H, s), 3.88 (3 H, s), 3.73 (3 H ,. s>,- ; 2, .4.9 (1 H t,, J = 2.4H z)---Product 3-9 b i--.

_{1 H-NMR (CDC 1 3} , "TMS) δ (ppm):

5 9 (1 H, s), 7.55 (2 H, .d, J; 8.2 Hz): 7,

J = 8.3 Hz), 6.85 (1-H, s-) 6.77 (2 H; .a, 2 5: 2 2 (JLH s), 4.35 ("1 H , dd-, J = 159 Hz, 2.2 Hz), 4.Ό .'- 9 (1 H; dd, J = 15.9 Hz, 2.2 Hz) ^ 3. 3H ,: s), 3.79 (3H, s), 3.68 (3Ή, s), 2.5.3 (1H, t, J = 2.4H z)

 Production example 3-1H-I:...-

--In the same manner as in Production Example '3 _ 8', use 4-methylsaldehyde 'instead of 4-methylsaldehyde' 0 'instead of Mobenzaldehyde ^: 2-methodyl-1.2- _ (4-bufenisle) Acetic acid was obtained. 2-Methoxy. 2- (4-Bromophene: / re) acetic acid 0.4,4 ;; 9 'g, product ΙΠ: 0.46 g of --9, 0.42 g of WSC and 0.4' 8 ml of pyridine was mixed and stirred at 115 for 5 hours. After cooling to room temperature, water was added to the reaction mixture, and extracted with ethyl acetate. The organic layer was washed successively with 5% hydrochloric acid, saturated aqueous sodium bicarbonate, water and saturated saline, dried over magnesium sulfate, dried and concentrated under reduced pressure, and the residue concentrated under reduced pressure was subjected to silica gel column chromatography. --The product of the following physical properties (hereinafter referred to as-, product 3-10a-) 0-20 g and-The product of the following physical properties (hereinafter, product 3-1 b-): 0 and 13 g were obtained. 1 '. Product 3-10 a-: ·-_---2: + ―

_{^{- 1 H- NMR- (CDC 1 3}} , TMS) δ (p pm):. .- 8. 3,4 (1-H, .br ..s), 7- 15 48 (2H, d, J = 8.3 Hz) 7.39 _ (-1: H, s), 7.3.3 (2 H, .d J- = 8.5 Hz), 6.80 (1 H, s), 6.70 to 6. 72 (2 H, m), 4.

7 2 (1H, s), 3.88 (6H-,--s), -3.70 (3H, s), 3.44 (3H, .- ^; s).

 -Raw 3—10 b,.

-(. P pm) 20 '^ H-NMR (CDC 1 3, TMS) δ: 8. 11 (1 Η, br - s.) J. -:. 58 (1H, s), 7. 54 (2H, d,-J. = 8.5 Hz, 7.34 (2 H, d.,. J = 8.3 Hz), 6.83 (1 H, d, J = 1..7 Hz) -6.75-(1 H,-d, one, J = 8.3 Hz), 6.71 (1H, dd, .J = 8.3 Hz, 17 H.z); 4; .:. -80 (1H, s), 3.90 (3H, s), 3.78 (3H, s), 3.67 (3H, 25s-), 3.44 (3H, s) s) ノ ―- .

-

... 2- (Naphthalene-1-yl) 1-2 (2, propynyloxy) acetic acid 0.54 g, 0.47 g of product ΙΠ-9, 0.4-2 g of WS C and pyridin .8 ml was mixed and stirred with 1'l ^ "5-5 for 5 hours. · After that, the mixture was cooled to room temperature, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. 5% hydrochloric acid, the layers - a saturated aqueous sodium bicarbonate solution, washed sequentially with water and brine. ^':.. after drying with sulfuric acid Maguneshiumu; and concentrated under reduced pressure, the residue silica force' gel - Ramukuroma - 'Togurafi one ..11 g: (hereinafter referred to as —, product 3—l: l .-- a ′) and products having the following physical properties 0: .15 g (hereinafter referred to as product 3-—11—b.)-'-...,. -ι'

 Product 3 1 l a--

¹ H-NMR (CDC 13, TMS) δ (pm) .: 8.43 (1 H, br.s), 7. ·-'”94 (1H, &), .7.78 1 to 7. -95 (3 H, m), MA.45 to 7.5-7 (3H-; .m), 7.-40 (1 H, s), 6.85 (: 1H, d, J; 2. 0 Hz), 6.74 (1 15 H, dd,. J = 8.0 Hz ゝ 2.0 Hz), 6.57 (lH,: d, J: = 8.0 Hz),.

 5-.34 (1H, s), 4.33 (1H, dd, · J = 15. '8-H z_ ,; 2.-4Ήz), 4.13 (1H, -dd, J = 15.8 Hz, 2.4 Hz), 3.87— :—( 3 H, s); 3.77 ”(3H, s), 3.62 (3Ή, s), 2.49 (1 H, s) t, J = 2.4H "z) ―-

20 Product 3— l i b. ― ''-.

.. Ή-NMR (CDC 13, TMS) δ. (Ppm): 8.25 (1 H,-b-r. S), .7--95 (1H, s), 7.- 8.0 to 7 91 (3H, m), 7.59 (lH, s), 7; •, 50 to 7.56 (3H, m), &. 87 (.1H, —d, J = l .. 9. Hz), 6.76 (.1-H, dd, J = 7.9 Hz, 1.9 Hz), 6.62 (1 H, d, J =: 7..9 Hz), 25 5.42 ( 1 H, s), 4v: 38 (1 H, dd,. J = 15.-8 H z, 2. .4 H z), 4.12 (1 H, d-d, J = 15.4 H z , 24Hz), 3.82 (3H, .s :), '3.74 (3H, s), -3.69 (3H, s), .2.54 (1H, t, J = 2 ._ 4H 'z) "'---

 Production Example 3-12-"---ノ

0.2-41 g of 2- (2-propynyloxy) -1-phenylacetic acid, 〇- of the product ΙΠ-9, 50 g, 0.456 g of WSC and 8 ml of pyridine. After stirring at 5 ° C, the mixture was cooled to room temperature, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was extracted with 0.5% hydrochloric acid, saturated aqueous sodium hydrogen carbonate; Washed sequentially with water and saturated saline, dried over magnesium sulfate, and concentrated under reduced pressure.The residue was subjected to silica gel chromatography, and the product having the following physical properties was obtained. 26 g-(hereinafter, referred to as ..product 3—Ha) 1 and a product exhibiting the following physical properties 0.05.8 g-(hereinafter, referred to as .product 3-1-b); Γ _; -10.--. ノ,--:. Raw-adult 3 ·-12 a "·,-:---";-"

^ H-NMR (CDC 13, TMS) δ (ρ ρ m): 8.38 (1 Η, br—. — S.),-: 7 ..— 30 to 7.46 (6 H, m) , 6 \ 74 ~ 690 (3H, -m),--516 (1H, s), 4.28-(1H, dd, J = 15.-, -6Ηζ, 2-4Hz) , — 4.07; (1 H, 15 dd, J = 15.6—Hz, 2.4 Hz),, 3., 87 (6H, s), .3-.6.8 (3.H, s) , 2.47-(1Ή, t, J = 2.

--'Product 3 -12 b —---, ■-...:--

^X H-NMR (CDC 13, TMS) δ (p pm): '8 .: 17 (1Η, -r., S), 7.1.5 (1H, s), 7.36 to 7. 50 (5 H, m), 6.79 to &. 90. (3 H, 20 m), 5.25 (1 H, s), 4.3-2 (lH, d--d, J = 15_. 7H-z, 2.4 Hz), 407 (1 H, dd, J = 15.7 Hz, 2.4 Hz), 3..8—9 (3Ή, s), 3.77 (3 H, s), 3-. 67 (-3H, ..s), 2 / 5-1 "(1H, t. J-2 24 Hz)

製造例 3— 1 3 . - . . ■■ :-·

Production example 3—1 3 .-..

 -In the same manner as in Production Example 3-8, 2-methoxy1-2-phenylacetic acid was obtained using z-noraldehyde in 4-methylthiobenzyl aldehyde. 0.42 g of 2-phenylphenylacetic acid, 0.49 g of the product ΙΠ-9 · -0.'no5 '8-g, -53 g of -WSCO.3 and 8 ml of pyridine The mixture was mixed and stirred at 115 ° C. for 5 hours. The mixture was cooled to room temperature and water was added to the mixture, followed by extraction with ethyl acetate. The organic layer was washed sequentially with '-5% hydrochloric acid, saturated aqueous sodium hydrogen carbonate, 7 and saturated saline, and dried over magnesium sulfate; and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and the product _0 ... 1-2 g (hereinafter, referred to as product 3-13 a) having the following physical properties and a product having the following physical properties were obtained. 0.9-G g '(hereinafter referred to as product 3-13 b). —.-...--: ；.-:.; ： ノ 一. Product 3― 1 3 a 1--...-:-ゝ '':-

_{^ H-NMR- (CDC 1 3} , TMS) δ (ppm),:. 8., 39 (. .1 HfL ^ br s), 7 3 0~7 44 (6 H, m), 6. 7 2 ~ 6, 8.5: (3H, m), ¾4 · 7; 5: 1: -H, s); — -3: 88 (3H, s), 3: 8.7— (3.H, s) , 2 3.6.5-: (3H, s), 3-- .4:-2 (3H, s). ·---. · ...-■-: '--.;-Product 3 — 1 3 b----― —- '. ―. —-

^ -NMR (CDC 13, TMS) δ "(ρ ρ ϊη) .: 8.15 (1 Η, brrs), Ί-, — 58 (1 H, s), 7.36-7, 50 (5 _; H, m), .6 7 9 to 6.87 (S Ή,), -4.83 (1 H, s), 3..89 (3H, s) :, 3.76 (3Ή, - s),: 3: - 6 5 (3H, s), 3. 42 (-3H s) - ':.::... over - - - - A -

Production Example 3—14 +. No-: No In the same manner as in Production Example 3—8, using 4-trifluoromethylbenzaldehyde instead of 4-methylbenzaldehyde, 2-methoxy One 2 -— (. 4-triphnoreolomethylphenyl) acetic acid was obtained. 70 g of 2-methoxy-2- (4-triol-la-methinorefenyl) acetic acid, 0.70 g of the product ΙΠ-9, 0.63 g of WS C and 10 ml of pyridine mixed, 1 1 5 ° C in · 6.beta争間¾ ^拌: the. Then: cooled to room temperature: water was added to the X anti-mixture and extracted with ethyl acetate. 5 Organic layer. The extract was washed successively with hydrochloric acid, saturated aqueous sodium hydrogen carbonate, water-and saturated saline, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel gel chromatography, and the products having the following physical properties were obtained. 1 g (hereinafter, referred to as product 3-14a) and 0.39 g of a product exhibiting the following physical properties (hereinafter, referred to as product 3-14b) were obtained. 1- · Product 3— 1 4 a--—- 'I-.

¹ H-NMR (CDC 1 a, TMS) δ · (ppm): 8.37, (lH br. — S), 7.- 1 ′ 58 to 7, 65 (4H, m), 7 :. 39. (1 H, s) ,: 6.80 (1 H, d, J-= 1.

5 H z), 6.6 5 to 6.7.3 (-.2 H-,-m),-4.—82 1 H,-s), 3.88 (3-1 H, s) 3 8 6 (3H, s), 3. '70 (3H, s), -3.47 (3Ή, s) 'Product S—1 4 b —...... ^{. - · .. 1 H - NMR} (CDC 1 3, - TMS) - δ (p pm) :: 8. 1.5. (1 Η ,. b: r · .- s), 7.

6 8 (: 2Ή, -d, J-= 8- .3H: 'z :), 7-. 6 0 _ (2H, -d., J = 8.0H z); .7. -5 8 ( l H, s-), 6-, 8 3. (1 Η, 'd, J. = 1.4 Hz), 6.68 ~ &:-7 5 (2

Production example 3—1 5--;; ':---

-2- (2, propynyloxy), 1--2- (5,6,7, .8-de: dora-'hydro-naphthalene-1-yl) acetic acid: 0.61 g, -0 :, 58. g of the product ΠΙ-_9, 0.53 g of WSC and 8 ml of pyridine were mixed and stirred at 115 for 6 hours. · After that, 'cool to room temperature, add water to the reaction mixture, and extract with ethinol acetate ^. -The organic layer was washed successively with 5% hydrochloric acid,-saturated aqueous sodium bicarbonate,-ice and saturated saline, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography. B 0.27 g of a product having the following physical properties (hereinafter, referred to as product 3-15a) and 0.46 g of a product having the following physical properties (hereinafter: 'Product · 3-15b ^: was obtained.

 Product 3—1 5 a '· · ·-

^{1 H-NMR "(CDC 1} 3, TM-S) δ. (. P p-rh :: - 8 3 6 teeth 1 H, b .r: s) , - 7 3 9 (1 H; s), .. 7. 00~7: 1 4 ( . 3.H m) / 6. 7 5 ~ -6, 8 8 (3 H, m), 5. '08 (1 H, s -), 4,: 25 (1 H, d, J = 1.5. .7 z, --¾ H. One z), '' 4: Ό 6. (ΪΗ, dd, J = 1 5.-7Hz; 2.4-Hz -), .-3.88 (-3H, -'s), 3.87 (3.H, s), 3.67 (3: H,; .. s), 2.67 -2.7 9 (4H, m), 2..45 (1 H, t, J = 2 ·· 4Hz),-1:: 7.5 ~: I. -8 1 (4H, m )- Product 3-- 1-57...-----.

_{^{1 H-NMR (GDC 1 3}} , TMS) δ (ppm) -: -.. 8 17 (. 1 Η, br: s) 7. 5 '9 (1 H7 s) 7. 05~ 7 · 16 ( 3 H, m) 6.80 to 6.91 (3 H, m); 5 .-- 16 (1H s), 4.29 29 (1 H, dd, J = 15.7 Hz, 2.4 2.z ) 4- ・ 04- (1 H dd, J = 15.7 H z, 2.4 H ¾)-3..89 (3 H,, s). 3.77-(. 3 H, s), 3. 7-0 (3 H, s) "2.70 to 2.81. (4H, m), 2v 50 (lH--t, J = 2.4H'z), 1.75 to 1. 84 (4H, m) ''

In the same manner as in Preparation Example 3-8, 4-methyl-benzaldehyde was used to produce 2-methoxy-1- (4-methyl-toxylphenyl). ) Acetic acid was obtained. 2-—Methoxy-2— (4-Methoxy-phenyl) acetic acid Ό, —49 g, 0.58 g of product IE-9, 0.53 g of WSC and pi ^: lysine: 8 m 1: ′ The mixture was stirred at 115 at 4 hours. After cooling to room temperature, water was added to the reaction mixture, and extracted with ethyl acetate. The organic layer was washed successively with 5% hydrochloric acid, saturated aqueous sodium hydrogen carbonate, -water and saturated saline, dried over magnesium sulfate, and concentrated under reduced pressure. : The residue is applied to silica gel column chromatography> Graphy, and the product has the following physical properties: 0._ 2.8 g- (hereinafter, product 3— .16 'a: and. 0.26 g of product showing physical properties (hereinafter referred to as -product 3-16 b)

 Got. — ■ + — · .-. '·.' ~ Product 3-16 a--—.

.. ^ H-NMR (CDC 13 , TMS) δ (ρ ρ m): 8. 38 (. 1 Η br s),: Ma.

 3 8 (1H, s), 7.33. (2H, d J = 8.7 Hz), 6.74 6.89 (5, H m), 4.70 (1 H, .s), 3.87 (6H, s.), 3: -69 (3H, "s"), 3..39 (3H, s)-.-.----

 Product 3— 16 b '-

_{^{1 H-NMR (CDC 1 3}} , TMS) δ / - (ppm): 8. 15 (1 H br ,. .s), .7: ,, "5 8 (lH, s), 7. 35 (- 2 H: d, J. = 8. -9Ή-ζ) 6.91_ (2 H d-J = 8.7 H .z), 6.8—5 to 6.88 (lH; .m), 6.80 to .83 (2 H; m), 4.7-8- (1H- -s), 3. & 9 (3H "s-). 3.82. (3H.s) 3 ..— .7 9 (3 H,-s-), 3.66 (3H, s), 3.39 (3 H—s). "—-:

• Production example 3—1 7--Production — In the same manner as in 8, use 4-methinolevenzaldehyde instead. 3 4-: Using 2-chlorobenzaldehyde, 2-methoxy 2— (3 4-Dichlorophenyl) acetic acid was obtained. 2-Methoxy-2- (3,4-dic-lororaenyl) acetic acid 0.5 g 9 g, product ΙΠ_9 0.58 "g WS C 0 ^.; '5.3.3 g and pyridi 8 ml Then, the mixture was stirred for 4 hours at −115 ° C. Then, the mixture was stirred at room temperature, cooled, and the mixture was added with water, and extracted with ethyl acetate: The organic layer was diluted with 5% hydrochloric acid saturated aqueous sodium bicarbonate; The residue was washed successively with brine, dried over magnesium sulfate, and concentrated under reduced pressure.The residue was subjected to gel chromatography.Ram 10 chromatography, 24 g of the product having the following physical properties , Product 3 ^ 1-7 a) and a product 0.1-1-2 g (hereinafter, referred to as product 3--17 b) having the following physical properties were obtained. . '-Product 3—17 a ■ ..,-:

^{-.. 1 H-NMR (} CDC 1 3, TMS) δ (p pm) :: 8 10 (1 br- s), 7. · 15 5 8 (1 H s), 57. (1 H d, J =-1-: 9 H z) 7.; 48 '(;;H-d,-"J = 8.2 H z) 7. 29 to 7. -3-3 (1 H .m): 6. 83 (1 Ή d, J. = 19 Hz.), 6.7-6 (lH, d,-J = 8.2 Hz) 6.59 U--Hdd J; 8. "-3 Hz , 2.0 Hz), 4.-79- (1 H, s), 3 89. (. 3 H,: s, 3._81 (3

H s), 3.69 (3H ¾), 3,-4 T (3H, s) '-'-

20 product 3— 17 b-—.

 ^ H-NMR (CDC 13, TMS) δ (p pm): 8..33 (ΙΗ, .- br.s) v..7.

 56 (1 H, s), 7..38 7.4.4 ('2Ή m)-7.-30 (1Ή' dd J =, 8.3 Hz, 1.7 Hz), 6.80 (lH, --d J = 1 .-- 5 Hz) 6.7TG ~ '6, 74 (2H, m), 4.71 (1H, s), .3_: 8-9 (6H, s), 3..75. (3H 25 s), 3.45 (3H, s)-,

次に、 本発明化合物の製造中間体の製造について参考製造例.を示す。 -,---

Next, reference production examples for producing intermediates for producing the compound of the present invention will be described.

 Reference Production Example 1-1

Sodium hydride (weight ⁰ / .; 60%) 6.8 g ethyl formate · 50 ml ί This is mixed. At 0 ° C, 2- (3,4-dimethyl ^: xyphenyl) acetonitrile N, N — ^; Dime-tilformamide solution (2- (3,4 di: me: dogisphenil). A mixture of '25-'g of acetonitrile and 30.ml of N, N-dimethylformamide) was added dropwise. The mixture was stirred at room temperature for 3 hours. Thereafter, diluted hydrochloric acid was added to the reaction mixture, and the mixture was extracted with ethyl acetate, and the organic layer was dried and concentrated. The obtained crystals were washed with hexane to obtain 22 g of 2- (3,4-dimethoxy, phenyl._n-yl) -13-hydroxyacrylonitrile. --'-—

 2- (3-, -¾-dimethoxyphenyl) 1-3-Hydroxyacrylonitrino: Torinole: — ·-.

.

Reference Production Example 1-2--1---1-- ^τ -'-Ethananol 100m 1, Hydroxylamine hydrochloride 3'. -7.g mixed at-0 ° C,-Sodium ethoxy Ethanol solution (weight% concentration; 20%) 18, was added. After stirring at around 0 ° C for 30 minutes, 10 g of 2- (3,4-dimethoxyphenyl) -13-hydroxyacrylonitrile is added, and at room temperature for 15 minutes, 75-8 (TC for 4 days at TC). Then, the mixture was allowed to cool to near room temperature, water was added to the reaction mixture, concentrated under reduced pressure, and then cooled forever, and the obtained crystals were washed with hexane, dried under reduced pressure, and dried under reduced pressure. 4 one (: 3, Zol

 :

(3 H, s)、 3. 9 (3H， s) 、 4. 60 (2H, b r)、 6. 84— 6. 9 1 (3H, m)、 8. 1

(3 H, s), 3.9 (3H, s), 4.60 (2H, br), 6.84—6.91 (3H, m), 8.1

— 6. (1 H, s)-....

 .... Reference Production Example 2: 1

 Bring 2 14 g of getyl carbonate to about 125 ° C, and gradually add 6.3 g of metal sodium.

Stir until the mixture is homogeneous, then slowly add a mixture of 30.0 g of 3 ', 4' · -dimethoxyacetophenone and 5.0 g of getyl carbonate, -140 ° C Stir with

-1. The reaction mixture is allowed to cool to around room temperature, and then a mixture of water and acetic acid (water acetic acid = 4

The mixture was separated by adding 1.), and the aqueous layer was extracted twice with getyl ether. Organic layer

Washed 3 times at 7k. The organic layer was dried and concentrated under reduced pressure. Silica gel chromatography of the residue

10 Attach to 3-(3,4-dimethoxyphenol) 1-3-oxo soap mouth

-5-5 g of ethyl ester were obtained. —. "-" '-"-"

:::

::

15

 -, 67-g of acetic anhydride, 3-5- (3,4-dimethoxyphenyl) -1-ethyl 3-oxo-propionate 55 g and ethyl 9-g-orthoformate are added, and 1-20 ° C For 2 hours and .14. For 5 hours. _ Thereafter, it was concentrated under reduced pressure to obtain 64 g of crude 2- (3,4-dimethoxybenzyl) -13-ethoxy, // ethyl acrylate.

 Ethyl ethoxyacrylate

一 -

one

 25 Reference Production Example 2-3.-· .- Ethanol 1 50m1 was mixed with the above crude 2-(-3,4-dimethoxybenzoyl) 3 •-■ "ethyl ethoxydiacrylate and methylhydrazine. After stirring at 40 ° C for 1 hour, the mixture was stirred at 40 ° C for 1 hour.The reaction mixture was concentrated under reduced pressure, and the residue was applied to silica gel. A product exhibiting physical properties (hereinafter referred to as product Π--3) 30 1 1 g was obtained.

 "Product Π— 3

. . ： „.； 参考製造例 2— 4 - . - . - - . ..' - - 生成物 Π— 3の 1 1 gと 2 0 %水酸化ナ hリゥム水溶液 1 1 gとをエタノール 3 0 m lに混合し、 7 0〜 8 0 °Cで 1時間攪拌した。室温付近まで放冷した反応混 合物に 5%塩酸を加えて p H 2付近として、 クロ口ホルムで 3回抽出した。 有機層 を乾燥じ、 減圧下濃縮して下記の物性を示す生成物 （以下、 生成物 Π— 4と記す） _{^{1 H-NMR (CDC 1 3}} , TMS) δ (p pm): -. 1- '3 0 (. 3H, t, J = 7.- - - 2 H z), 3. 9 2 (3H, s ), One 3.94 (3H, s), 3.94 (3H, s), 4.2.5 (2H, q, J = 7., 2Hz) 6.9: 1 (1 H, d, J = 8.4Hz), 7.35 4 1-7.43 (2H, m), 7,. _: 94 (1H, .s)

: „.; Reference Production Example 2—4-.-.--..'--11 g of product III-3 and 1 g of 20% aqueous sodium hydroxide solution in ethanol 3 The mixture was stirred for 1 hour at 70 to 80 ° C. The reaction mixture was allowed to cool to around room temperature, and 5% hydrochloric acid was added to adjust the pH to around 2, and the mixture was extracted three times with chloroform. The organic layer is dried and concentrated under reduced pressure to give a product having the following physical properties (hereinafter referred to as product Π-4)

1 1 g was obtained. -'. I.:--.—:.--Product Π— 4--. —. —--I—H— NMR (CDC 13, TMS) -δ. (H z): 3.: 9 2 (6 H, s), 3.96 (3 d, J = 8-.8 Hz, 7.40-7.43 (2 H, m), "

 Reference Production Example 2-5-:-.--. Hexane 6 Om 1 was mixed with 5.-8 g of product Π-4, and thionyl chloride 3 m 1 was added. Stirred. The reaction mixture allowed to cool to around room temperature was concentrated under reduced pressure to obtain a crude product. ■ '-:

 The above crude product was mixed with 3Om1 of tetra-t-drofuran, and 3.9 g of a 28% aqueous ammonia solution was added at 0 ° C, followed by stirring at room temperature for 3 minutes. -The reaction mixture was concentrated under reduced pressure to obtain a product having the following physical properties (4.8 g, hereinafter referred to as product Π-5).

Thus, a product having the following physical properties (hereinafter, referred to as product II-16a): 3. lg was obtained. Product Π-— 6 a---., ： .

 -In a mixture of 16 ml of water and 10 ml of tetrahydrofuran, 4.5 g of the product polymer and 0.40 g of lithium hydroxide are mixed and stirred at room temperature for 2 hours. This. 10 ml of the aqueous solution of τΚ potassium oxide (3 mol / 1) was added, and the mixture was stirred under reflux for 2 days. : 'The reaction mixture was acidified with dilute hydrochloric acid and extracted with ethyl acetate. The organic layer was dried and concentrated under reduced pressure. The obtained crystals were washed with hexane to obtain 3.'5 g of a product having the following physical properties (hereinafter, referred to as -product 8-8a). -:--Product II-1 8a---.:

¹ H-NMR (CDC 1 a, TMS) δ (ppm): 1.44 (9H, s), 3.85 (3H, s), 3.94 (3H, s), 6 — 77 (1H, d, J = 1— .6 Hz.), 6.84 (1 H, dd, J = 1.6 Hz, 7.9 Hz), 689 (1H, d, J = 7.9 H z), -7. 95 (1H, s)-

CH3O-

CH3O 'Reference Production Example 3—1--·-:, １----

A mixture of 9.3 g of ethyl 4-methylphenyldaloxylate and 13 ml of an aqueous sodium hydroxide solution (wt%; 30%) in 30 ml of ethanol is stirred under reflux for 2 'hours:

 = 8.3 H z) '-.

 Reference Production Example 3-2--;-"

(34-Dimethoxyphenyl) acetonitrile 40.0 g- and methyl formate & 8: g were mixed with dimethylformamide 40 Om 1. -Gum (weight / pa. 60%) 11 g was gradually added, followed by stirring at room temperature for 3 hours. Thereafter, water was added to the reaction mixture at about 0- ° C., and the mixture was washed with t-tert-butyl methyl ether. : 5% hydrochloric acid was added to the 層 layer until it was about Η_Η2, and extracted with ethyl acetate. Dry the organic layer—Hydoxydari Lonito Linoleni

9 1 (6 H, m);

0 g. And isocyanate mixture I ^, concentrated under I pressure at ° C, crude

 2- (3; 4-Dimethoxyphenyl) -1-3-hydroxyatarilotril 2.5.5 g and .triethylamine 2.3 ml and tetrahydro? The mixture was added to furan 3 Orii 1 at a temperature of 0.5 ° C. at 0.5 ° C., and 3 g of the crude 0.4-methylphenyl-glyoxyl acid chloride was added, followed by stirring at room temperature for 3 hours. Thereafter, water was added to the reaction mixture: concentrated under reduced pressure, and extracted three times with chlorophoronelem. The organic layer was dried and concentrated under reduced pressure. The residue was subjected to chromatography to give a product having the following physical properties :: 18 g (below, product ΠΙ-3a) and 1.0 2 g-(hereinafter, product 13 b) ) Were obtained.

Product ΙΠ— 3 a. — '· "'-― One _{NMR - (CDC 1 3, -} TMS) δ (p pm): 2. 43 (3H, s), 3. .8.8 (3- Ή, one s), 3. 90 - (3H , s) , .3. 96 (3H, -s), 6.90-6 .. 96 (3H, m), 7.29 (2H, d, J = 8.4 Hz), 7.46 (1H, . s) 8. 3 6 (2H , d, - J = 8 4H z), 8. 96 (1H ,. s) - " generated ΙΙΠ_ 3 b - -:. · ifi two NMR (CDC 1 _3, TMS) 8 (ppm) ·: 2..4-6 (3H, s), 3.84

1 H-NMR (CDC 1₃, TMS) δ (p p m).： 2. 47 (1 H, . t., J = 2. 4Hz)、 2. 51 (1 H, t , J =2. 4Hz), .4.-18 (1 H, d-d, J = 2. , 4 H z , 16. 2Hz)、 4. 31 (1 H, -d d-， ] = 2.— 4Ή z，· 16·. :2Hz:) .

_{1 H-NMR (CDC 1 3} , TMS) δ (ppm) .: 2. 47 (1 H,. T., J = 2. 4Hz), 2. 51 (1 H, t, J = 2. 4Hz) , .4.-18 (1 H, dd, J = 2., 4 H z, 16.2 Hz), 4.31 (1 H, -d d-,] = 2.—4Ή z, · 16 ·. : 2Hz :).

4.67 (1H, dd, J = 2.4Hz, 15.4: jH-z), 4.76 (1H, dd-1, J = 2.4Hz, 15.4-Hz) , 5, 23 (lH, 's), 7.33-7.42 _ (4 H, m). No.. — · ·': Two Reference Production Examples 3-7-. Methyl 2- (4-propynyloxy) -2- (4-chlorophenyl) acetate: -2'-; (2-propynyloxy) —2- (4-chlorofudinyl) acetic acid (2-p-ppinyl). Is dissolved in 800 ml of tetrahydrofuran, and an aqueous solution of lithium hydroxide (a mixture of 6.74 g of lithium hydroxide and 28 Om 1 of water) is added dropwise at 0 ° C .: The mixture was stirred at 0- ° C to room temperature for 3 hours. Thereafter, the reaction mixture was diluted with hydrochloric acid and extracted with ethyl acetate. The organic layer is dried, concentrated under reduced pressure, and the obtained crystals are washed with hexane to give -2- (2-propynyloxy) -2- (4-chlorophenyl) acetic acid 4 — 3.4 g. -■

Niloxy) 1 2-'(4--phenyl-)-Acetic acid'-',-

¹ H-NMR (CDC 13, TMS) 8 (pp: 2..5.1 (1 H, t, J 2 '4H z), 4.15 (1 H, "dd, J = 2.- 4 H z , 16.0 H z) 4..32 (1 H, dd, J = 2.4 H z, 16.OH-z), 5.20 Cl H, s), 7, 3 3-7 . ·-, — 4 4 (4 H, m), 8.70—9.50 (1 H 'br) ·-

10 Reference Manufacturing Example 3-8.

 2-(3,4-Dimethoxyphenyl-) 1 .3 -Hyd P.xia-Chloronitrile 6 ... '5 g is dissolved in ethanol and .tert-Butylhydrazine hydrochloride 5. 9 g and 3 g of sodium hydrogencarbonate were added, and the mixture was stirred under reflux for 1 hour. The reaction mixture was allowed to cool to around room temperature, filtered, and the filtrate was concentrated under reduced pressure. The residue 'was subjected to silica gel chromatography (extended solvent: hexane Z, ethyl acetate = 1/1) to give a product having the following physical properties (hereinafter,...).

 .

-7 5-6. 9 '20-

-.

 2-(3,4-Dimethoxyphenyl) 1-3-Hydroxyacrylonitrino P5.0 g and methylhydrazine 1.35 g are mixed with 50 ml of ethanol, and then mixed at 75-80- ° C 25-. Stir for 3 hours. Thereafter, the reaction mixture was concentrated under reduced pressure, and to the resulting residue was added hegisan, followed by filtration. The obtained crystals were washed with hexane to give the product (hereinafter referred to as product ΠΙ.9). "5.17 g were obtained. -. · '-Product ΠΙ— 9 "

_{^{. 1 H- NMR (CDC 1 3}} , TMS) δ (ppm): 1/8 2 (2 H, br: s), - OCH 3 - - one;

CH ₃ ― 3.73 (1: 8H, s), 3..74 (1.2 H, s), -3.89-; 3; 90 (6 m), 6.8 "8-6.98 (3H, s) m), ——7.22 (0.4 H, s), 7.4 ”1 (0.

6 M, .s) '1-Reference production example 3-10-Reference production example 3-In the same manner as in 4 to 3-7, use 4-monobromofurin in place of methyl 4-chloro-mouth phenyldaryloxylate. Methyl enylglyoxynolate was used to obtain 2- (2- (4-bromophenyl acetic acid.-. ")-2 (4-Bromophenyl) acetic acid

d d， Γ = 2..4 Η ζ 16. OH z)、 4. 3—2— (1 Μ, d d, J =2. 4 Hz, 16-. 0H z)、 5. 一 9 — (1H， ' s)：、 7. 52 2.TMS) δ (ρ ρ m): -2.51 (1 H, t, J = 2

dd, Γ = 2..4 Η ζ 16. OH z), 4.3−2— (1 ,, dd, J = 2.4 Hz, 16-. 0Hz), 5.1-9 — (1H, 's) :, 7.52 2.

H, d, J = 8.3 Hz)-, 7.3-(2H, d,-J = 8: -3 Hz), -9.32. (: H, b r)

ノ マ ス、シヮム 0. 86 gに、 2—プロ ΐナフタレンのテトラヒ ドロフラン溶液（2 ーブロモナ-フタレン 7. 0 gとテトラヒ ド.口フラン 22m 1 との混合溶液） を室温 で滴下し、 30分間撹拌し—た。該混合液を一 0 °Cに冷却し、シュゥ酸ジェチル 9 gおよびテ—トラヒ ドロフランの混合物を徐 .に滴下した。 該混合液-を 2時間かけ -て室温まで昇温し、.飽和塩化アンモニゥム水を加えて、 酢酸ェチルで抽出した。 得 られた有機層を飽和炭酸水素ナトリゥム水および飽和食塩水で洗浄し、 無 ·7_Κ硫酸マ. グネシゥムで乾燥した後、.減圧 Τで濃縮した 得られた残渣をシリ.力ゲルカ ク ,口 トグラフィーに付し、 （ナフタレン一 2—ィル)' ダリオキシル酸ェチル 9. 3 • gを得た。— . " -

A solution of 2-propanaphthalene in tetrahydrofuran (a mixture of 7.0 g of 2-bromona-phthalene and 22 ml of tetrahydrofuran) was added dropwise to 0.86 g of nose and shim at room temperature for 30 minutes. Stirred. The mixture was cooled to 10 ° C., and a mixture of 9 g of getyl oxalate and tetrahydrofuran was gradually added dropwise. The mixture was allowed to warm to room temperature over 2 hours, saturated aqueous ammonium chloride was added, and the mixture was extracted with ethyl acetate. The obtained organic layer was washed with saturated sodium bicarbonate water and saturated saline, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the resulting residue was dried with silica gel. The resulting mixture was subjected to chromatography to obtain 9.3 • g of (naphthalene-1-yl) 'ethyl dalioxylate. —. "-

(Naphthalene 1 ^ 2 ^),,, rioki, ethyl rulate-;-

^X H-NMR (CDC 1 a, TMS) —δ (ρ ίη)-: 8 56 (1 Η, s)., 8-. —05 (1 Η, dd, J = 1.7 Η ζ, 8. 5Η ζ-), .7- :.: 9.8 (1Η, · d, J = 8.2Η ζ): 7.93 (1Η, d, J = 8: 7-Η · ζ) ·,- 7..85 (1 Η, d, J = 8.2 Η ζ 7.56-7.60 (1: Η, m), Τ .. 03-7.07 (1 Η, m), 4.5 1 (2Η, q,] =?. 2Η ζ), 1.47:. (3Η, t J = 7.2Hz) Reference Manufacturing Example 3-12--

-Reference example 3-In the same way as-.

The following compounds were obtained using ethyl (naphthalene-2-niyl) glyoxylate instead of methyl. -.-. "

 2-(Naphthalene-2-yl) 2-7 dro _ethyl ethyl xyacetate .- '. ·

-· ',.-;

 'H-NMR (; CDC 1 a, TMS) δ (ρ pm): 7.91 (1 Η, s), .82-7.86. (3 H, m) \ 7.47-7%' 53 : \ (3H, m-), 5.32 (1H, d,

J = 5.6Hz), 4.13-4. 3-2 (2H, m), ■ 3.56 (1H, d, J = 5.

6 Hz), 1.22 (3H, t, J ^: = 7.6 Hz)-

2-(Naphthalene-2-inole)-2. Methane 'ethyl ethyl sulfonylodidiacetate' :.

- - . - ノ - - ： -' :.

--.-No--:-'

_{NMR (CDC 1 3, TMS)} ; δ (ppm): 7. 96 (1 H, s 7. 84 " one 7 90 (3H, m), 7. .51- 7. '56 (3 H, m) , 6.09 (1H, s), 4.L 9-4.32 (2H, m) :, -3-. 10 (3.H, s), -l. 24 (3H, \ tT "j

':, "·'-'..: ヽ:-; ·,'-:

2-(Naphthalene-2-yl) _ 2--2'-propynyloxy), acetic acid ^ tilester and 2- (naphthalene _2-yl) 1-2--(2-vinyl oxy) 'acetic acid -: ('2 Propinyl) Mixture with ester-.---: _--. -.--:

_{- NMR - (CDC 1 3,} TMS) δ (p pm I) ":. -. 7 95, ( 1 H, s :) ,: 7 -83: one 7. 87 (3 H, m) , 7. 49—7.5.8 (3H, m), 5.43. (0.:5H, s), 5.39 (0.5H, s), -4: 79 '(0.5H , dd, J = 2. 4Hz, 1 5Hz), 4. 66 (0. 5 H, dd J- = 2 4 H z, 15 H z), one ^{4:. l 2 4::} 38 (3H, m ), 2.49-2. 52- (lH, m), '2.43 (0, 5, t, J- -2.4 Hz), 1.22 (1.5 H, t, J = 7.- 1 Hz)--.-.-2 '' (1-naphthalene 2 f) 1- 2- (2-propynyloxy) acetic acid--..: 1 ·

¹ H-NMR's _{CDC 1 3 TMS) δ (ppm} ) 8- 10 (H, br) - 7. 9 3 1 H, s) \ 7. 83- 7. 88 (3H m) ,: 7. 49- 7 53 (3H, m)-

5.4.0 (1 H, s), 4.37 (1H dd J = 2: 4Ήζ16 H z)-4, 1 5 (1 H, dd, J = 24 H z 1 "6 H z) 2.53 ( 1 H, t,] = 2:

Hz).

 Reference Production Example 3 13 ―--, ―.

 Reference Production Example 3-4 In the same manner as in 3-7, the following compounds were obtained, respectively, using phenylidalioxynoleic acid ethinole instead of methyl 4-hydroxyphthalate-oxynoleate. . ·---,:?

-2—Hide.Mouth-Xii-2-Fetinoleacetate--.. ·-.-One--'· ■ ”· .:”-, —

¹ H-NMR (CDC 13, TMS) δ (ppm) 7.29— 7. + 4-5— (5 H m) 5.15 (1 Η, s 4. 1 1—4 · 30- (2Η, m 3 .... 50. (1 H, br) 1.22 (3H, t, J = 7.OH z)

2 _ methanesulfonyloxy feninole acetate

_{^{1 H-NMR (CDC 1 3}} , TMS) δ (p pm):.. 7. 28-7; 46 (5Η, m), 5. 92 (1 H, s), -4 16-4 "3 1 (2H, m), 3: 08. (3H, s) ;; 1.24 (3H, t, J = 7.1Hz) '

 , 2- (2-Propinyloxy) — a mixture of 2-ethyl phenylacetate and 2 (2-propyninoleoxy) —2-phenyl-2-acetic acid (2-probuyl)

_{. LH-NMR (CDC 1 3} , - TMS) δ- (p pm) -: -7 44- 7. 48 (2H, - m 7. 36- 7. 39 (3H, m 5. 29 (0. 5H , s 5.1 9 (0.5H, s 4.78 (0.5H dd, J = 2.4 Hz 15H z 4.66 (0.5 H, dd, J = 2.4 Hz, 15 Hz), 4.09—4.34 (3H, m), 2..47—2.50 (1 H, -m), —2.45 ( 0.5H, t., J = 2.4Hz), t. '2,2 (1, 5H, t, J = 7.1Hz:'-

2- (2-propynyl-oxy) -2-phen, nilacetic acid

^ H-NMR δ (p pm ). (CDC 1 3, TMS.): 8- 10 (1H, br), 7. 3 .6- 7. 47 (5 H, m), 5. 23 (lH. , —S,), 4.33 (1H, dd,] = -2. 4-Hz, 16Hz), 4 · 13 (1H, dd,: -J2 2 · 4Ήz,. 16—H ' )., _ 2.5, 1 (1H, t, J = 2.4Hz) .-.--

Ten

 —-Examples of preparations are shown below. Here, “parts” indicates “parts by weight”. -: No. Formulation Example 1-:.

---Product 1-1, 2-1, 2-2 ,: 23-; 2-4, 2-5, 2-6, 2-7, 2 "1-8, 3-1, 3- 2, 3-3, 3-4, ^ 1 5, 3-6, 3-7a, 3_7b, -15 3-8a, 3-8b, 3-9a, 3_9b, 3 — _ 10a, 3—10b, 3—lla, —3——llb, 3—12a, .3—12b, 3—3a, 3—13b, -3—1.4a, 3 no 1-14b, 3-15a, 3-: 15b., 3.-16a, 3-16b, 3-17a, and 50 parts of 31Jb, 3 parts of calcium lignesulfonic acid, A wettable powder is obtained by crushing and mixing 2 parts of magnesium lauryl sulfate and 45 parts of synthetic hydrous silicon oxide 20 Formulation Example 2----; ·-.

 Product 1-1-1, 2--1, 2--2, 2 .-- 3, 2--4, 2--5, 2--6, 2-7,2-One-eight, 3--1, 3--2, 3- 37- 3 -4, 3——5, 3—.6, 3—7a, .3—7b, -3—8a—, 3—8b, 3— & a, 3—9b,. 3-10 a, 3.-l Q b, 3- 1 1 a ;.-.. 3. 1 llb, 3-12 a, .3 12 b,-3-13 a, 3--13 b, 1 3-14a, 3-25: 20 parts of 14b, -3-15a-, 3-15, 3-16a, 3-16b, 3-1.7a and 3-17, ~ 17b And 1.5 parts of sorbitan trioleate are mixed with 28.5 parts of an aqueous solution containing 2 parts of polyvinylino alcohol and finely pulverized by a wet pulverization method. 05 parts and Al: 'Medine Magnesium Silicate' Ό. Including 1_ parts-: Add 40 parts of aqueous solution, add 10 parts of ropireng 'recall and mix with stirring. L 30 Flowable formulation obtain. "

: Formulation example 3-.-':-. No.-.--. Product 1-1, 1, 2-1, 2, 2_, 2-3, 2-4,' 2-5, 2-6 ., 2-7, 2 1-1 8, 3 1 1, 3 1 2, 3-3,.: 3 1 4., 3-5, 3-&& 3: .- 7 _a ,: 3 1 7-b, --.. 3-8 -a 3— 8 b 3— 9 a 3 9. b. 3— 10. a- 3—10, 3— 1 1a; 1—3—1 1b 3— 12 a 3 12 b,-3-13 a, 3-1.3 b 3-14 a, 3-14 b 3-15 a-3-15 b 3-16 a, 3-16 b 3-17 a and 3--17 b 2 parts / 88 parts of kaolin clay and 10 parts of talc are mixed well by grinding. -.-.

 -Formulation Example 4--..-

-— Product 1— 1 2— 1 2— 2 2— 3 2— 4 2—5 2— 6 2—7 2. One 8.3—1—3—2 3—3—3—4 3—5 3 — 6 3— 7 a 3-7 b 3-8 a, 3— 8 b 3 -9 a, 3— 9 b 3— 1 h a 3— 10 b 3-1 1 a, 10 3— 1— 1 b 3- 12. a \ 3— 12 b -3— 13 a 3— 13 b 3-1 a- ,; 3 ..

 14 b 3-15 a; 3— 15 b 3 _ 16 a 3— 1—6 b 3—1 7-a, and 5 parts of .3: .- 17 b, polyoxyethylene styryl phenyl An emulsion is obtained by well mixing 14 parts of ter, 6 parts of calcium dodecyl-benzenesulfonate and 75 parts of benzene and benzene. .:---.

15 Formulation example 5 ''-.-

"Product 1—1 2—1 2—2—2—3: 2—4 2—5 2-6, 2-7—-8 3—1 3—2 3—3 —3—-4 3—5 3— 6 3— 7 a-3— 715 3— 8 a 3— 8 b 3— 9 a 3-9 b 3— 10—a 3 1-10 b 3-1 1 a-3-1 1 b. 3 — 1—2 a 3— 12 b 3—13 a, 3—13 b ,; 3—14 a 3 20—14 b 3—15 a 3——15 b 3—16 a; —3—16 b ′ 3--17a and: 2 parts of 3-_- 1-b, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lydanine sulfonate, 30 parts of beta-tonite and 30 parts of kaolin clay-63 parts After pulverizing and mixing well, add water. Knead, granulate and dry to obtain granules.

-Formulation Example 6------.,-.-

25 Products 1—1 2 _ ί, 2—2, 2—3 2, 4 2—5 2—-6 2—7, .2- ー 8 3-1, 1, 3—2 3—3—, 3— 4 -3— 5.3. 3 — 6 3 .. 7 a 3-7 b .. 3 — 8 a, · 3 — 8, 3 — 9 a, 3 — '9 b .3 — 10- a, —3 — 10— b 3 1 1.1 a-.. 3— llb 3_ 12 a 3— 12 b, 3— 13 3-a 3 _ 13 b, .3— 14 a .— 3, — 14 b 3— 15 a 3 — 15 b; 3— 16 a 3 .—— 1 part of 16 b, 3-17 a and 30-17 b; polyoxyethylene anoyl ether sulfate ammonium. 35 parts of white carbon containing 50 parts of salt 'And 55 parts of water are mixed and finely pulverized by a wet pulverization method to obtain a' floor veneer preparation '. :: .. ::. ■ — —--: Next, test examples show that the compound of the present invention is useful for controlling plant diseases. —-. 35 The control effect was determined by visually observing the area of the lesion on the test plant at the time of the investigation, and determining the area of the lesion in the untreated plot and the area of the lesion in the plot treated with the compound of the present invention. Were evaluated by comparison. -Test example 1------

Plastic pots were filled with sandy loam, tomatoes-(variety: -Ponteroza) were sown, and-grown in a greenhouse for 20 days. Products' 2-1, .2-2, 2. ^-3, 2-4, 2-7,

 2—8, 3—3, 3—4, 3—5, 3—7a, 3._7b, −3—8a, 3—8b, 3—9a, 3—9b, — 3—10a, 3—11a, 3—llb, 3—12a, 3—12b, 3—13a, 3—13b—, 3—1—4a, 3—15a, 3-15b, 3-16a-, .3-16b, .3-17a and 3-17b were prepared according to Formulation Example 6. A diluted solution was prepared such that the concentration of the compound of the present invention was 50.0 ppm in the above procedure. The diluted solution was sprayed on the foliage of the above-described tomato seedlings so as to adhere to the leaves. After spraying, the plants were air-dried and sprayed with an ice suspension of zoospores of tomato late blight (approximately 10,000 Zml) (at a rate of about 2 m-1 per plant). 23.T: Tomato seedlings were cultivated for one day under the condition of relative humidity of 90% or more, and then transferred to a greenhouse at 2.4 ° G in the day and 20 ° C at night for 4 days. The above products 2-1 and 2-2 2 _

3, 2-4, 2-7, -2-8, -3-3, 3-4 3-5, 3-7a, 3-7b, 3_8a-, 3_8b, 3-9a, — 3 9 b, 3— 10 a. ゝ 3— lla, 3— llb,

-.3—12a, 3_12b, 3_13a, 3—13b, 3-14a, 3-15a, 3-15b, 3—16a, 3—16b, -3—1.7a In addition, the lesion area on the plant to which the diluted solution of 3-17b was sprayed was 10% or less of the lesion area in the untreated plot.

 Test Example 2 · · · · · ·----.

 _Plastic pots were filled with sandy loam, and grape (variety: Veri 一)-was sown and grown in a greenhouse for 40 days. Products 1-1, 2-3, 2-4, 2-7, 2-8, 3-0.3, 3-4, 3_5, 3_-6, 0.3_7a, 3.-7 b-., 3-8 a, 3-9 a :, 3, -9 .. b, 3-12 a, 3-15 a, and 3-15 b are prepared. After the preparation, a diluent was prepared with water so that the concentration of the compound of the present invention was 200 ppm. The diluted solution was sprayed on the foliage so as to sufficiently adhere to the grape leaf surface. Next, the sprayed liquid on the leaf surface was air-dried, and then a suspension of zoosporangia of grape downy mildew was spray-contacted. After inoculation: cultivated for 2 days under conditions of 0.3 ° C and a relative humidity of 90% or more, then moved to a greenhouse at 24 ° C in the daytime and at night at 2. Q ° C for 6 days. ,-

Then, the lesion area on the plant was visually observed. The lesion area on the plant was investigated. Product 1 Ryo.:! , 2-3, 2-4, 2-7, 2-8, -3-3, 3-4, 3-5, 3-6, 3-7a, -3-7b, 3-8a, 3-9a, 3_9-b, -3—12a, 3-15a, and 3-15. Less than 10% of the area: -I-Industrial applicability---... The compound of the present invention has an excellent plant disease controlling effect, and an effective amount of the compound of the present invention can be applied to plants. Alternatively, plant diseases can be controlled by treating soil or soil. '--

Claims

The scope of the claims 1. Equation (1) Or (E)

X ¹ represents an OR ⁴ group, Y ¹ represents a hydrogen atom, or represents a = 0 group or = NOR ⁵ group together with X 1 iY ¹ ; R ¹ Represents a hydrogen atom, a halogen atom, a C 1 ^ 3 alkyl group, a C 1 C 3 haloalkyl group or a C 1 C 3 alkoxy group; represents a hydrogen atom, a halogen atom or a C 1 -C 3 alkyl group. R ¹ and R ² together represent a trimethylene group, a tetramethylene group or a CH = CH—CH CH group; R ³ represents a C 1 -C 3 alkyl group or Represents C 3 -C 4 alkynyl group, R- ⁴ is hydrogen atom, C 1 one C 3 Anore - represents Kill group or C '3 -C 4 alkynyl group, R ⁵ is C 1 one - C 3 alkyl group. Or a C 3 -C 4 alkynyl group. An amide compound represented by--. .- 2. The amide compound according to claim 1, wherein in the formula (1), is a hydrogen atom, a halogen atom, or a C I_C 3 alkynole group. 3. In equation (1) ',

3. The amide compound according to claim 2, which is: 4. In equation (1):

3. The amide compound according to claim 2, which is: 5. In equation (1),-: '

3. The amide compound according to claim 2, which is: 6: In the formula (1), — X ¹ is an OR ′ ¹ -group, and Y ¹ is a hydrogen atom, or X ¹ and Y ¹ are combined to form a NOR ⁵ group. An amide compound according to item 3, .4, or 5. - 7. The amide compound according to claim 3, wherein in the formula (1), X ¹ is an OR ⁴ group, and Y ¹ is a hydrogen atom. … '·-. 8. The mid compound according to claim 3, 4 or 5, wherein in the formula (1), X ¹ is an OR ⁴ group, Y ¹ is a hydrogen atom, and R is a hydrogen atom. . _.,-.- 9. In the formula (1), X ¹ is an OR ⁴ group, and Y ^{1 is a} S hydrogen atom :: R ⁴ is a C 1 -C 3 alkyl group. 6. The amide compound according to 5. -10 · 'Formula (1), wherein X- ¹ is an OR ⁴ group, Y ¹ is a hydrogen atom, and R ⁴ is a C 3 -C 4 alkynyl group. 5. The amide compound according to 5. . 1 1. formula (1), X ¹ and Y ¹ Do the guard cord -.. Connexion = NOR ⁵ -. A group according Koko ■ The amide compound described in 3, 4, or 5. 1 2. In the formula (1), X ¹ and Y ¹ are joined together to form a = N.OR ⁵ group, and 2 is a C 1 -C 3 alkyl group. The amide compound described. 1 3. The amide compound according to claim 1, wherein in the formula (1), R ³ is a C 1 -C 3 alkyl group. .:-- 1 4. The amide compound according to claim 1, wherein in the formula (1), R ³ is a C 3 -C 4 alkyl group. -.  15. A fungicidal composition comprising the amide compound according to any one of claims 1 to 14 and a carrier. --; ...  16. A method for controlling plant diseases, which comprises applying the amide compound according to any one of claims 1 to 14 to a plant or soil. ^-'