WO2018167677A1

WO2018167677A1 - Novel dithiolane compound or a salt or an n-oxide and use thereof

Info

Publication number: WO2018167677A1
Application number: PCT/IB2018/051686
Authority: WO
Inventors: Surendra Kumar KUMAWAT; Manish Kumar SINGH; Pramod Kumar CHAUHAN; Amit CHOUHAN; Md. Jawed Ashraf; Bhupender Kumar SATOLIYA; Ananya TIWARI; Tetsuya Imai
Original assignee: Oat & Iil India Laboratories Private Limited
Priority date: 2017-03-15
Filing date: 2018-03-14
Publication date: 2018-09-20
Also published as: AR111179A1; TW201837025A

Abstract

An object of the present invention is to provide a dithiolane compound or a salt or an N-oxide thereof that controls diseases. The present invention provides a dithiolane compound represented by Formula (1) or a salt or an N-oxide thereof, wherein R1 represents hydrogen, halogen, C1-6 alkyl or a substituent as defined herein; R2 represents hydrogen, halogen, C1-6 alkyl or a substituent as defined herein; R3 represents hydrogen, halogen, C1-6 alkyl or a substituent as defined herein; Y1 represents optionally substituted aryl, optionally substituted pyridyl or a substituent as defined herein; Y2 represents optionally substituted aryl, optionally substituted pyridyl or a substituent as defined herein; Q represents cyano or a substituent as defined herein.

Description

DESCRIPTION

Title of Invention: NOVEL DITHIOLANE COMPOUND OR A SALT OR AN N-OXIDE AND USE THEREOF. Technical Field

The present invention relates to a novel dithiolane compound or a salt or an N-oxide and a process for preparing the same. The invention further provides an agricultural and horticultural fungicide composition comprising the said compounds .

Background Art

In recent years, for the protection of plants against diseases caused by fungi, various known fungicides are being used. However, due to long term and heavy use of these fungicides, development of resistance in various fungi has been observed. As a result, the control of drug resistant fungi could not be accomplished by the use of known

fungicides. Consequently, there is a demand for the

development of new types of compounds having a fungicidal activity against drug resistant fungi.

WO 2015/003991 (Patent Literature (PTL) 1) discloses the compounds represented by the formula (A) :

(A) wherein, X is 0, S or NR⁴; Y and Z are independently O, S, NR⁵ or C(R⁶R⁷); A is hydrogen, alkyl, haloalkyl, cycloalkyl, halocycloalkyl , aryl, heteroaryl, various electron-withdrawing groups like, nitro, cyano, acetyl, carboxy, or the like; Q is alkyl, haloalkyl, cycloalkyl, aryl, heteroaryl, heterocyclic group, or the like; R¹, R² and R³ are independently hydrogen, halogen, Ci_₆ alkyl, Ci_₆ haloalkyl, C₃_₇ cycloalkyl, Ci_₆ alkoxy, Ci-6 haloalkoxy, or optionally substituted phenyl. The

publication also mentioned that the compounds represented by the Formula (A) are useful as fungicide to control plant diseases .

Patent literature WO 2015/162271 (Patent Literature (PTL) 2) and WO 2015/162269 (Patent Literature (PTL) 3) also disclose imidazole substituted compounds represented by the Formula (B) :

wherein, X and Y are independently 0, S or NR⁵; R¹ , R² and R⁴ are independently hydrogen, halogen, Ci-6 alkyl, Ci_₆ haloalkyl, Ci-6 cycloalkyl, Ci-6 alkoxy, Ci-₆ haloalkoxy; R³ is phenyl, which is substituted by at least one substituent R⁶ or an aromatic five-membered heterocycles; and R⁵ is hydrogen, Ci_₆ alkyl, alkoxy, or Ci_₆ cycloalkyl .

The publications also mentioned that the compounds represented by the Formula (B) are useful as fungicide to control plant diseases. However, these publications nowhere disclose the compounds of the present invention.

Further Patent literature WO 2015/162268 (Patent

Literature (PTL) 4) also disclosed imidazole substituted compounds represented by the Formula (C) :

wherein, X and Y are independently 0, S or NR⁴; R¹, R² and R³ are independently hydrogen, halogen, C_X-₆ alkyl, Ci-6 haloalkyl, C -6 alkoxy, Ci-₆ haloalkoxy Z¹, Z², Z³, Z⁴ and Z⁵ are

independently CR⁵ or N.

The publication also mentioned that the compounds represented by the Formula (C) are useful as fungicide to control plant diseases. However, this publication nowhere discloses the compounds of the present invention.

Citation List

Patent Literature

PTL 1: WO 2015/003991

PTL 2: WO 2015/162271

PTL 3: WO 2015/162269

PTL 4 : WO 2015/162268 Summary of Invention

Solution to Problem

The present invention provides novel dithiolane compound or a salt or an N-oxide which exhibit excellent fungicidal activity against drug resistant fungi as well as drug

sensitive fungi.

The present invention also provides a process for preparing the said dithiolane compound or a salt or an N- oxide.

The present invention further provides a new type of fungicide for agriculture and horticulture which exhibits a remarkable fungicidal effect against chemical-resistant fungi as well as chemical-sensitive fungi. Specifically the present inventors conducted extensive research, and succeeded in synthesizing a compound represented by the following Formula (1) or a salt or an N-oxide thereof that has fungicidal activity. The present inventors have conducted further research based on the above findings. The present invention has ;thereby been accomplished.

More specifically, the present invention includes the following embodiments:

Item 1:

A dithiolane compound represented by Formula (1)

or a salt or an N-oxide thereof,

wherein R¹, R² and R³ are identical or different and each represents hydrogen, halogen, Ci-₆ alkyl, Ci_₆ haloalkyl, Ci_₆ alkoxy, Ci-e haloalkoxy, Ci-6 alkoxy Ci_₆ alkyl, Ci-6 haloalkoxy Ci_₆ alkyl, C₂-6 alkenyl, C₂_₆ haloalkenyl, C₂_₆ alkynyl, C₂_₆ haloalkynyl, C₃-₈ cycloalkyl, C3-8 cycloalkyl Ci-6 alkyl, optionally substituted aryl, optionally substituted

heteroaryl, or optionally substituted heterocyclic group, two of R¹, R² and R³ groups, taken together, may form a ring, via or not via at least one heteroatom, the groups represented as R¹, R², and R³ may optionally be further substituted;

Y¹ represents optionally substituted aryl, optionally substituted pyridyl, optionally substituted pyrazinyl, optionally substituted pyrimidinyl or optionally substituted pyridazinyl ;

Y² represents optionally substituted aryl or optionally substituted heteroaryl; and

Q represents hydrogen, nitro, cyano, Ci_₆ alkyl, Ci_₆ haloalkyl, C₃-₈ cycloalkyl, C₃-₈ cycloalkyl Ci_₆ alkyl, Ci_₆ alkylcarbonyl , Ci_6 haloalkylcarbonyl , C₃-₈ cycloal kylcarbonyl , Ci-6 alkoxycarbonyl , Ci_₆ haloalkoxycarbonyl , C₃_₈

cycloalkoxycarbonyl , Ci_₆ alkylthio, Ci_₆ haloalkylthio, C₃-₈ cycloalkylthio, C₃_₈ cycloalkyl Ci-₆ alkylthio, Ci-₆ alkoxy Ci-6 alkylthio, Ci-₆ alkylsulfonyl , Ci_₆ alkylsulfinyl, Ci_₆

haloalkylsulfonyl , Ci_₆ haloalkylsulfinyl , C₃__g

cycloalkylsulfonyl , C₃-₈ cycloalkylsulfinyl, C₃_₈ cycloalkyl Ci_₆ alkylsulfonyl , C₃-₈ cycloalkyl Ci-₆ alkylsulfinyl, optionally substituted arylthio, optionally substituted aryl Ci_₆

alkylthio, optionally substituted arylsulfonyl , optionally substituted arylsulfinyl , optionally substituted aryl,

optionally substituted heteroaryl, or optionally substituted heterocyclic group.

Item 2:

The dithiolane compound or a salt or an N-oxide thereof according to Item 1, wherein R¹, R² and R³ are identical or different and each represents hydrogen, halogen, or Ci_₆ alkyl.

Item 3:

The dithiolane compound or a salt or an N-oxide thereof according to any one of the preceding items, wherein R¹, R² and R³ are identical or different and each represents hydrogen or Ci-6 alkyl.

Item 4:

The dithiolane compound or a salt or an N-oxide thereof according to any one of the preceding items, wherein Y¹ is optionally substituted aryl or optionally substituted pyridyl Item 5:

The dithiolane compound or a salt or an N-oxide thereof according to any one of the preceding items, wherein Y¹ is a phenyl ring represented by Y^la:

wherein R⁴, R⁵, R⁶, R⁷ and R⁸ are identical or different and each represents hydrogen, halogen, nitro, cyano, hydroxyl, formyl, optionally substituted amino, Ci-6 alkyl, Ci_6

haloalkyl, Ci_₆ alkoxy, Ci-6 haloalkoxy, Ci-₆ alkoxy Ci-6 alkyl, Ci_₆ haloalkoxy Ci_₆ alkyl, Ci-6 alkoxycarbonyl , Ci_s

haloalkoxycarbonyl , cyano Ci-6 alkyl, cyano C]-₆ alkoxy, C₂-e alkenyl, C₂_₆ haloalkenyl, cyano C₂-₆ alkenyl, C₂-₆ alkynyl, C₂-₆ haloalkynyl, cyano C₂-₆ alkynyl, C₃-₈ cycloalkyl, C3-8 cycloalkyl C -6 alkyl, Ci-₆ alkylthio, Ci-6 haloalkylthio, C₃-₈

cycloalkylthio, C₃_₈ cycloalkyl Ci-6 alkylthio, Ci_₅ alkoxy Ci-₆ alkylthio, Ci-₆ alkylsulfonyl , Ci_₆ alkylsulfinyl , Ci_₆

haloalkylsulfonyl, Ci^₆ haloalkylsulfinyl, C₃_₈

cycloalkylsulfonyl , C₃-₈ cycloalkylsulfinyl , C₃_₈ cycloalkyl, Ci 6 alkylsulfonyl , C₃_₈ cycloalkyl Ci_₆ alkylsulfinyl , C₂~₆

alkenyloxy, C₂_₆ alkynyloxy, C₂-6 haloalkenyloxy, C₂-e

haloalkynyloxy , Ci~e alkylsulfonyloxy, Ci_6 alkylsulfinyloxy, Cj 6 alkylcarbonyl , Ci-6 haloalkylcarbonyl , carboxyl, OCN, SCN, SF₅, optionally substituted aryloxy, optionally substituted aryl Ci-6 alkoxy, optionally substituted arylthio, optionally substituted aryl Ci_6 alkylthio, optionally substituted arylsulfonyl , optionally substituted arylsulfinyl , optionally substituted heteroaryloxy, optionally substituted

arylsulfonyloxy, optionally substituted arylsulfinyloxy, optionally substituted aryl, optionally substituted

heteroaryl, or optionally substituted heterocyclic group; and the * is the point of attachment to the parent compound.

Item 6:

The dithiolane compound or a salt or an N-oxide thereof according to any one of the preceding items, R⁴, R⁵, R⁶, R^; and R⁸ are identical or different and each represents hydrogen, halogen, Ci_₆ alkyl, Ci-6 haloalkyl, Ci-₆ alkoxy or Ci_₆

haloalkoxy .

Item 7 :

The dithiolane compound or a salt or an N-oxide thereof according to any one of the preceding items, wherein Y¹ is optionally substituted 4-pyridyl, optionally substituted 3- pyridyl, or optionally substituted 2-pyridyl. Item 8: The dithiolane compound or a salt or an N-oxide thereof according to any one of the preceding items, wherein Y¹ is a pyridine ring represented by any one of Y^lb, Y^lc and Y^ld:

wherein R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴ , R¹⁵, R¹⁶, R¹⁷, R¹⁸ , R¹⁹, and R^: are identical or different and each represents hydrogen, halogen, nitro, cyano, hydroxyl, formyl, optionally

substituted amino, Ci_₆ alkyl, Ci_₆ haloalkyl, C_X-₆ alkoxy, C₁-₆ haloalkoxy, Ci_₆ alkoxy Ci_₆ alkyl, Ci_₆ haloalkoxy Ci_₆ alkyl, Ci-6 alkoxycarbonyl , Ci-₆ haloalkoxycarbonyl, cyano Ci_₆ alkyl, cyano Ci-₆ alkoxy, C₂-₆ alkenyl, C₂-₆ haloalkenyl, cyano C₂~6 alkenyl, C₂-6 alkynyl, C₂~6 haloalkynyl, cyano C₂_₆ alkynyl, C₃-₈ cycloalkyl, C₃-₈ cycloalkyl Ci_₆ alkyl, Ci^₆ alkylthio, Ci-6 haloalkylthio, C₃-₈ cycloalkylthio, C₃-₈ cycloalkyl Ci_₆ alkylthio, Ci_₆ alkoxy Ci_₆ alkylthio, Ci_₆ alkylsulfonyl , Ci_₆ alkylsulfinyl, Ci_₆ haloalkylsulfonyl , Ci_₆ haloalkylsulfinyl , C3-8 cycloalkylsulfonyl , C₃_₈ cycloalkvlsulfinyl, C₃_₈

cycloalkyl, Ci-₆ alkylsulfonyl , C₃_₈ cycloalkyl d-₆

alkylsulfinyl , C₂_₆ alkenyloxy, C₂_₆ alkynyloxy, C₂_₆

haloalkenyloxy, C _₆ haloalkynyloxy, Ci_₆ alkylsulfonyloxy, Ci_₆ alkylsulfinyloxy, Ci_₆ alkylcarbonyl , Ci-₆ haloalkylcarbonyl , carboxyl, OCN, SCN, SF₅, optionally substituted aryloxy, optionally substituted aryl Ci_₆ alkoxy, optionally substituted arylthio, optionally substituted aryl Ci-₆ alkylthio,

optionally substituted arylsulfonyl , optionally substituted arylsulfinyl, optionally substituted heteroaryloxy, optionally substituted arylsulfonyloxy, optionally substituted

arylsulfinyloxy, optionally substituted aryl, optionally substituted heteroaryl, or optionally substituted heterocyclic group; and

the * is the point of attachment to the parent compound. Item 9:

The dithiolane compound or a salt or an N-oxide thereof according to any one of the preceding items, wherein R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹,and R²⁰ are identical or different and each represents hydrogen or halogen.

Item 10:

The dithiolane compound or a salt or an N-oxide thereof according to any one of the preceding items, wherein Y¹ represents:

wherein the * is the point of attachment to the parent compound . Item 11:

The dithiolane compound or a salt or an N-oxide thereof according to any one of the preceding items, wherein Y¹ represents :

wherein the * is the point of attachment to the parent compound.

Item 12:

wherein the * is the point of attachment to the parent compound .

Item 13:

The dithiolane compound or a salt or an N-oxide thereof according to any one of the preceding items, wherein Y² is optionally substituted aryl.

Item 14:

The dithiolane compound or a salt or an N-oxide thereof according to any one of the preceding items, wherein Y² is a phenyl ring represented by Y^2a:

(Y^2a)

wherein R , R , R , R , and R are identical or

different and each represents hydrogen, halogen, nitro, cyano, hydroxyl, formyl, optionally substituted amino, Ci-6 alkyl, Ci_ haloalkyl, Ci-6 alkoxy, Ci_₆ haloalkoxy, Ci_₆ alkoxy Ci_₆ alkyl, Ci-6 haloalkoxy Ci-6 alkyl, Ci-6 alkoxycarbonyl, Ci_₆

haloalkoxycarbonyl, cyano Ci-₆ alkyl, cyano Ci_₆ alkoxy, C₂-₆ alkenyl, C₂_₆ haloalkenyl , cyano C₂_₆ alkenyl, C₂-₆ alkynyl, C₂-₆ haloalkynyl, cyano C₂~e alkynyl, C₃-₈ cycloalkyl, C₃_₈ cycloalkyl Ci-6 alkyl, Ci_₆ alkylthio, Ci_₆ haloalkylthio, C₃-₈

cycloalkylthio, C₃-₈ cycloalkyl Ci-₆ alkylthio, Ci_₆ alkoxy Ci-₆ alkylthio, Ci-₆ alkylsulfonyl, Ci_₆ alkylsulfinyl , Ci_₆

haloalkylsulfonyl , Ci-6 haloalkylsulf inyl, C3_₈

cycloalkylsulfonyl , C₃_₈ cycloalkylsulfinyl, C₃-₈ cycloalkyl, Ci 6 alkylsulfonyl, C₃-₈ cycloalkyl Ci-₆ alkylsulfinyl, C₂-6

alkenyloxy, C₂-₆ alkynyloxy, C₂_₆ haloalkenyloxy, C₂_₆

haloal kynyloxy , Ci-6 alkylsulfonyloxy, Ci-₆ alkylsulfinyloxy, Ci 6 alkylcarbonyl, C ₆ haloalkylcarbonyl , carboxyl, OCN, SCN, SF₅, optionally substituted aryloxy, optionally substituted aryl Ci-₆ alkoxy, optionally substituted arylthio, optionally substituted aryl Ci-6 alkylthio, optionally substituted

arylsulfonyl, optionally substituted arylsulfinyl , optionally substituted heteroaryloxy, optionally substituted

Item 15:

The dithiolane compound or a salt or an N-oxide thereof according to any one of the preceding items, wherein R²¹, R²², R²³, R²⁴, and R²⁵ are identical or different and each represents hydrogen, halogen, nitro, cyano, optionally substituted amino, Ci-g alkyl, Ci-₆ haloalkyl, Ci-6 alkoxy, C ₆ haloalkoxy, or optionally substituted aryl.

Item 16:

The dithiolane compound or a salt or an N-oxide thereof according to any one of the preceding items, wherein Y² is optionally substituted heteroaryl.

Item 17:

The dithiolane compound or a salt or an N-oxide thereof according to any one of the preceding items, wherein Y² is optionally substituted pyridyl, optionally substituted pyrazinyl, optionally substituted pyrimidinyl, optionally substituted pyridazinyl or optionally substituted thiazolyl.

Item 18:

The dithiolane compound or a salt or an N-oxide thereof according to any one of the preceding items, wherein Y² is optionally substituted pyridyl, optionally substituted pyrazinyl, or optionally substituted thiazolyl.

Item 19:

The dithiolane compound or a salt or an N-oxide thereof according to any one of the preceding items, wherein Y² is optionally substituted pyridyl.

Item 20:

The dithiolane compound or a salt or an N-oxide thereof according to any one of the preceding items, wherein Y² is optionally substituted 4-pyridyl, optionally substituted 3- pyridyl, or optionally substituted 2-pyridyl.

Item 21:

The dithiolane compound or a salt or an N-oxide thereof according to any one of the preceding items, wherein Y² is a pyridine ring represented by any one of Y^2b, Y^2c and Y^2d:

and R are identical or different and each represents

hydrogen, halogen, nitro, cyano, hydroxyl, formyl, optionally substituted amino, Ci_₆ alkyl, Ci-6 haloalkyl, Ci-6 alkoxy, Ci-6 haloalkoxy, Ci_₆ alkoxy Ci-₆ alkyl, Ci-₆ haloalkoxy Ci-6 alkyl, Ci_ 6 al koxycarbonyl , Ci_₆ haloalkoxycarbonyl , cyano Ci_6 alkyl, cyano Ci-6 alkoxy, C₂_₆ alkenyl, C₂_₆ haloalkenyl, cyano C₂-e alkenyl, C₂-e alkynyl, C₂-₆ haloalkynyl, cyano C₂-6 alkynyl, C₃_₈ cycloalkyl, C₃_₈ cycloalkyl Ci ₆ alkyl, Ci_₆ alkylthio, Ci_6

haloalkylthio, C₃-₈ cycloalkylthio, C₃_₈ cycloalkyl Ci-6

alkylthio, Ci_₆ alkoxy Cj_._₆ alkylthio, Ci_₆ alkylsulfonyl, Ci_₆ alkylsulfinyl , Ci_₆ haloalkylsulfonyl, Ci_₆ haloalkylsulfinyl , C₃-₈ cycloalkylsulfonyl , C₃-₈ cycloalkylsulfinyl, C₃_₈

cycloalkyl, Ci-6 alkylsulfonyl , C₃_₈ cycloalkyl Ci_₆

alkylsulfinyl , C₂~e alkenyloxy, C₂-e alkynyloxy, C₂-6

haloalkenyloxy, C₂_₆ haloalkynyloxy, Ci_₆ alkylsulfonyloxy, Ci-6 alkylsulfinyloxy, Ci-₆ alkylcarbonyl , Ci^₆ haloalkylcarbonyl , carboxyl, OCN, SCN, SF₅, optionally substituted aryloxy, optionally substituted aryl Ci_₆ alkoxy, optionally substituted arylthio, optionally substituted aryl Ci_₆ alkylthio,

optionally substituted arylsulfonyl , optionally substituted arylsulfinyl , optionally substituted heteroaryloxy, optionally substituted arylsulfonyloxy, optionally substituted

the * is the point of attachment to the parent compound. Item 22 :

The dithiolane compound or a salt or an N-oxide thereof according to any one of the preceding items, wherein R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, R³², R³³,

R³⁵, R³⁶, and R³⁷ are identical or different and each represents hydrogen or halogen.

Item 23:

The dithiolane compound or a salt or an N-oxide thereof according to any one of the preceding items, wherein Y² is selected from the group consisting of:

the * is the point of attachment to the parent compound.

Item 24 :

A dithiolane compound selected from the group consisting of compounds lc-1, lc-2H, lc-2L, lc-3, lc-3H, lc-3L, lc-4H, lc-4L, lc-SL, lc-6L, lc-8, lc-8H, lc-8L, lc-9, lc-9H, lc-9L, lc-lOH, lc-lOL, lc-HH, lc-llL, lc-13H, lc-13L, lc-14H, lc- 15H, lc-16, 1C-16H, lc-19, lc-20, lc-23, lc-23H, lc-23L, lc- 24, lc-24H, lc-25H, lc-25L, lc-26, lc-26H, lc-26L, lc-27H, lc- 28L, lc-29H, lc-29L, lc-30H, lc-32H, lc-32L, lc-33, lc-34H, lc-34L, lc-35, lc-35H, lc-35L, ld-ΙΗ, ld-6H, ld-6L, ld-13, ld- 17, ld-17H, ld-17L, le-3, and le-7, or a salt or an N-oxide thereof .

Item 25:

A dithiolane compound selected from the group consisting of compounds lc-2H, lc-2L, lc-3, lc-3H, lc-3L, lc-4H, lc-4L, lc-5L, lc-6L, lc-8, lc-8H, lc-8L, lc-9, lc-9H, lc-9L, lc-lOH, lc-lOL, lc-HH, lc-13H, lc-13L, lc-14H, lc-15H, lc-16, lc-16H, lc-19, lc-20, lc-23, lc-23H, lc-23L, lc-24H, lc-25H, lc-25L, lc-26, lc-26H, lc-26L, lc-27H, lc-29H, lc-29L, lc-32H, lc-32L, lc-33, lc-34H, lc-34L, lc-35, and lc-35H, or a salt or an N- oxide thereof.

Item 26:

A dithiolane compound selected from the group consisting of compounds lc-1, lc-ΙΗ, lc-lL, lc-2H, lc-2L, lc-3, lc-3H, lc-3L, lc-4H, lc-4L, lc-5H, lc-5L, lc-6, lc-6H, lc-6L, lc-7H, lc-7L, lc-8, lc-8H, lc-8L, lc-9, lc-9H, lc-9L, lc-lOH, lc-lOL, lc-HH, lc-llL, lc-13H, lc-13L, lc-14H, lc-15H, lc-15L, lc-16, lc-16H, lc-16L, lc-17H, lc-18L, lc-19H, lc-19L, lc-20, lc-21H, lc-21L, lc-22H, lc-23, lc-23H, lc-23L, lc-25H, lc-25L, lc-26, lc-26H, lc-26L, lc-27H, lc-27L, lc-28H, lc-28L, lc-29H, lc- 29L, lc-30H, lc-30L, lc-31H, lc-31L, lc-32H, lc-32L, lc-33, lc-34H, lc-34L, lc-35, lc-35H, lc-35L, lc-36, lc-37, lc-37, lc-40H, lc-40L, lc-41H, lc-41L, ld-1, ld-ΙΗ, ld-lL, ld-12, ld- 13 and ld-13L, or a salt or an N-oxide thereof. Item 27 :

A dithiolane compound selected from the group consisting of compounds lc-1, lC-16, lc-16H, lc-16L, and lc-19H, or a salt or an N-oxide thereof. Item 28:

A dithiolane compound selected from the group consisting of compounds lc-1, lc-lL, lc-2H, lc-2L, lc-3, lc-3H, lc-3L, lc-4H, lc-4L, lc-5H, lc-5L, lc-6, lc-6H, lc-6L, lc-8, lc-8H, lc-8L, lc-9, lc-9H, lc-9L, lc-ΙΟΗ, lc-lOL, lc-HH, lc-llL, lc- 12, lc-12H, lc-13, lc-13H, lc-13L, lc-14H, lc-15H, lc-15L, lc- 16, lc-16H, lc-16L, lc-17H, lc-18L, lc-19, lc-19L, lc-20, lc- 21H, lc-21L, lc-23, lc-23H, lc-23L, lc-24, lc-24H, lc-25H, lc- 25L, lc-26, lc-26H, lc-26L, lc-27H, lc-30L, lc-32H, lc-32L, 1C-34H, lc-34L, lc-35, lc-35H, lc-35L, lc-37, lc-37L, lc-38H, lc-38L, lc-44, lb-5L, ld-ΙΗ, ld-lL, ld-6L, ld-7, ld-7H, ld-7L, ld-8, ld-11, ld-llH, ld-HL, ld-12L, ld-15, ld-16, ld-16H, ld- 16L, ld-17, ld-17H, and le-6, or a salt or an N-oxide thereof.

Item 29:

A plant disease-controlling agent containing the

dithiolane compound or a salt or an N-oxide thereof according to any one of Items 1 to 28.

Item 30:

A fungicide containing the dithiolane compound or a salt or an N-oxide thereof according to any one of Items 1 to 28.

Advantageous Effects of Invention

A dithiolane compound or a salt or an N-oxide thereof according to the present invention achieves an excellent fungicidal effect on fungal plant pathogens. Additionally, the dithiolane compound or a salt or an N-oxide thereof according to the present invention is useful as a new type of fungicide that exhibits excellent fungicidal activity not only against chemical-sensitive fungi, but also against chemical-resistant fungi .

Description of Embodiments

Hereinafter, the present invention will be described in more detail with reference to examples, but the technical scope of the present invention is not limited to these

examples. Throughout the entire specification, a singular expression should be understood as encompassing the concept thereof in the plural form, unless specifically noted

otherwise. Thus, singular articles (e.g., "a", "an", "the" and the like in case of English) should also be understood as encompassing the concept thereof in the plural form unless specifically noted otherwise. Further, the terms used herein should be understood as being used in the meaning that is commonly used in the art, unless specifically noted otherwise. Thus, unless defined otherwise, all terminologies and

scientific technical terms that are used herein have the same meaning as the terms commonly understood by those skilled in the art to which the present invention pertains. In case of a contradiction, the present specification (including the definitions) takes precedence.

A dithiolane compound or a salt or an N-oxide thereof The invention provides a dithiolane compound or a salt or an N-oxide thereof represented by the Formula (1) for use in agriculture and horticulture.

Wherein R¹, R², R³, Y¹, Y² and Q are as defined above. The presence of one more possible asymmetric carbon atoms in a compound of Formula (1) means that the compounds may occur in optionally isomeric form, i.e. enantiomeric or diastereomeric forms. The presence of one or more possible double bonds in a compound of Formula (1) means that the compounds may occur in various diastereomeric forms.

Thus, the structure:

means both forms, namely the Z-form and the E-form:

(1-1) (1-11)

Also atropisomers may occur as a result of restricted rotation about a single bond. Formula (1) is intended to include all those possible isomeric forms and mixtures thereof. The present invention includes all those possible isomeric forms and mixtures thereof for a compound of Formula (1). Likewise, Formula (1) is intended to include all possible tautomers. The present invention includes all possible tautomeric forms for compound of Formula (1) .

Next, the terms in the present specification are

described below. In the present specification, the number of substituents of a group defined by "optionally substituted" or

"substituted" is not particularly limited if it is

substitutable , and is one or plural. In addition, unless otherwise indicated, the description for each group is also applied when the group is one part of or a substituent on other groups.

"Ci-6 alkyl" means a linear or branched, saturated hydrocarbon group having one to six carbon atoms.

"C₂-6 alkenyl" means a linear or branched, unsaturated hydrocarbon group having two to six carbon atoms and

containing one to three double bonds.

"C₂-6 alkynyl" means a linear or branched, unsaturated hydrocarbon group having two to six carbon atoms and

containing one triple bond.

"C3-8 cycloalkyl" means a cyclic alkyl having three to eight carbon atoms, and includes those cyclic alkyls having a partially bridged structure.

"Ci-6 alkoxy" refers to a "Ci_₆ alkoxy group", and the "Ci_6 alkyl" moiety is defined the same as the above-described "C ₆ alkyl" .

"Aryl" means a monocyclic or polycyclic aromatic

hydrocarbon .

"Heterocyclic" means a saturated, unsaturated, or aromatic heterocyclic group which has at least one of nitrogen, oxygen, phosphorus and/or sulfur atoms in the ring and may be bonded at any substitutable position.

"Heteroaryl" means an aromatic heterocyclic group which has at least one of nitrogen, oxygen, and/or sulfur atoms in the ring and may be bonded at any substitutable position, wherein the ring member atoms of the heteroaryl include besides carbon atoms 1, 2, 3 or 4 heteroatoms selected from N, 0 and S.

The following shows specific examples of each group as used in this specification.

Examples of halogen include, but are not particularly limited to, fluorine, chlorine, bromine, iodine, and the like.

Examples of Ci-6 alkyl include, but are not particularly limited to Ci_6 straight-chain or branched-chain alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec- butyl, tert-butyl, n-pentyl, n-hexyl, and the like.

Examples of Ci-6 haloalkyl include, but are not

particularly limited to Ci-6 straight-chain or branched-chain alkyl substituted with 1 to 9, preferably 1 to 5, halogen atoms, such as fluoromethyl , chloromethyl , bromomethyl, iodomethyl, difluoromethyl , 2 , 2-difluoroethyl ,

trifluoromethyl, 2 , 2 , 2-trif luoroethyl , pentafluoroethyl ,

3,3, 3-t rifluoropropyl , 4,4, -trifluorobutyl ,

heptaf luoroisobutyl , and the like.

Examples of Ci-6 alkoxy include, but are not particularly limited to Ci-₆ straight-chain or branched-chain alkoxy, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,

isobutoxy, sec-butoxy, tert-butoxy, and the like.

Examples of 0ι__δ haloalkoxy include, but are not

particularly limited to Ci-6 straight-chain or branched-chain alkoxy substituted with 1 to 9, preferably 1 to 5, halogen atoms, such as fluoromethoxy, chloromethoxy, bromomethoxy, iodomethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2- trifluoroethoxy , pentafluoroethoxy, 3, 3, 3-trifluoropropoxy, 4 , 4 , 4-trifluorobutoxy, heptafluoroisobutoxy, and the like.

Examples of Ci-6 alkoxy Ci_₆ alkyl include, but are not particularly limited to alkoxyalkyl in which Ci~₆ straight- chain or branched-chain alkyl is substituted with Ci_₆

straight-chain or branched-chain alkoxy, such as

methoxymethyl , ethoxymethyl , n-propoxymethyl ,

isopropoxymethyl , n-butoxymethyl , isobutoxymethyl , sec- butoxymethyl , tert-butoxymethyl , methoxyethyl , ethoxyethyl, methoxy-n-propyl , methoxy-n-butyl , and the like.

Examples of Ci_₆ haloalkoxy Ci-6 alkyl include, but are not particularly limited to straight-chain or branched-chain alkoxyalkyl substituted with 1 to 9, preferably 1 to 5, halogen atoms, such as fluoromethoxymethyl ,

chloromethoxymethyl , bromomethoxymethyl , iodomethoxymethyl , difluoromethoxymethyl , trifluoromethoxymethyl , 2,2,2- trifluoroethoxymethyl , and the like. Examples of C ₈ cycloalkyl include, but are not

particularly limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like.

Examples of C₃-₈ cycloalkyl Ci-6 alkyl include, but are not particularly limited to, cyclopropylmethyl , cyclobutylethyl , cyclopentylmethyl , cyclohexylmethyl , and the like.

Examples of Ci-6 alkylcarbonyl include, but are not particularly limited to, Ci-6 straight-chain or branched-chain alkylcarbonyl groups, such as methylcarbonyl (acetyl), ethylcarbonyl (propionyl), n-propylcarbonyl (butyryl),

isopropylcarbonyl ( isobutyryl ) , n-butylcarbonyl (valeryl), isobutylcarbonyl ( isovaleryl ) , sec-butylcarbonyl , tert- butylcarbonyl , and the like.

Examples of Ci_6 haloal kylcarbonyl include, but are not particularly limited to, Ci-6 straight-chain or branched-chain alkylcarbonyl substituted with 1 to 9, and preferably 1 to 5, halogen atoms, such as fluoromethylcarbonyl ,

chloromethylcarbonyl , bromomethylcarbonyl , iodomethylcarbonyl , dichloromethylcarbonyl , trichloromethylcarbonyl ,

difluoromethylcarbonyl , trifluoromethylcarbonyl ,

chlorodifluoromethylcarbonyl , bromodifluoromethylcarbonyl , dichlorofluoromethylcarbonyl , 2,2, 2-trichloroethylcarbonyl, 2, 2, 2-trifluoroethylcarbonyl, pentafluoroethylcarbonyl, and the like.

Examples of C_X-6 alkoxycarbonyl include, but are not particularly limited to, Ci-6 straight-chain or branched-chain alkoxycarbonyl groups, such as methoxycarbonyl ,

ethoxycarbonyl , n-propoxycarbonyl , isopropoxycarbonyl , n- butoxycarbonyl , isobutoxycarbonyl , sec-butoxycarbonyl , tert- butoxycarbonyl , and the like.

Examples of C ₆ haloalkoxycarbonyl include, but are not particularly limited to, Ci_₆ straight-chain or branched-chain alkoxycarbonyl substituted with 1 to 9, preferably 1 to 5, halogen atoms, such as fluoromethoxycarbonyl ,

chloromethoxyca bonyl , bromomethoxycarbonyl ,

iodomethoxycarbony1 , dichloromethoxycarbony1 ,

trichloromethoxycarbonyl , difluoromethoxycarbonyl ,

trifluoromethoxycarbonyl, 2,2, 2-trifluoroethoxymethyl, pentafluoroethoxycarbonyl , 3, 3, 3-trifluoropropoxycarbonyl , 4, 4, 4-trifluorobutoxycarbonyl , heptafluoroisopropoxycarbonyl , and the like.

Examples of C3-8 cycloal kylcarbonyl include, but are not particularly limited to, cyclopropylcarbonyl ,

cyclobutylcarbonyl , cyclopentylcarbonyl , cyclohexylcarbonyl , and the like.

Examples of C₃-_a cycloal koxycarbonyl include, but are not particularly limited to, cyclopropyloxycarbonyl ,

cyclobutyloxycarbonyl , cyclopentyloxycarbonyl ,

cyclohexyloxycarbonyl , and the like.

Examples of cyano Ci-6 alkyl include, but are not particularly limited to, Ci-6 straight-chain or branched-chain alkyl substituted with a cyano group, such as cyanomethyl, cyanoethyl, cyano-n-propyl , cyano-isopropyl , cyano-n-butyl , cyano-isobutyl , cyano-sec-butyl , cyano-tert-butyl , cyano-n- hexyl, and the like.

Examples of cyano C s alkoxy include C₁-₆ straight-chain or branched-chain alkoxy substituted with a cyano group, such as cyanomethoxy , cyanoethoxy, cyano-n-propoxy, cyano- isopropoxy, cyano-n-butoxy , cyano-iso-butoxy , cyano-sec- butoxy, cyano-tert-butoxy , cyano-hexyloxy, and the like.

Examples of C2-6 alkenyl include, but are not particularly limited to, vinyl, allyl, 2-butenyl, 3-butenyl, 1-methylallyl , and the like.

Examples of C2-6 haloalkenyl include, but are not

particularly limited to, 2 , 2-dichlorovinyl , 2 , 2-dibromovinyl , 2 , 2-difluorovinyl , 3 , 3-difluoro-2-allyl , 4 , 4 -difluoro-3- butenyl, 4 , 4 , - tri fluoro-2-butenyl , and the like.

Examples of C2-6 alkynyl include, but are not particularly limited to, ethynyl, 2-propynyl (propargyl) , l-methyl-2- propynyl, 1-butynyl, 2-butynyl, 3-butynyl, and the like.

Examples of C₂-e haloalkynyl include, but are not

particularly limited to, fluoroethynyl , bromoethynyl ,

chloroethynyl , iodoethynyl, 3 , 3 , 3-trifluoro-l-propynyl , and the like.

Examples of cyano C₂-e alkenyl include, but are not particularly limited to, 2-cyanovinyl , 2, 2-dicyanovinyl, 3- cyano-2-allyl, 3, 3-dicyano-2-allyl, 4 -cyano-3-butenyl , 4,4- dicyano-3-butenyl , , , -tricyano-2-butenyl, and the like.

Examples of cyano C₂~6 alkynyl include, but are not particularly limited to, cyanoethynyl , 3-cyano-l-propynyl , and the like.

Examples of Ci-₆ alkylsulfonyl include, but are not particularly limited to, Ci-6 straight-chain or branched-chain alkylsulfonyl groups, such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl , isopropylsulfonyl , n-butylsulfonyl ,

isobutylsulfonyl, sec-butylsulfonyl , tert-butylsulfonyl , and the like.

Examples of Ci-6 haloalkylsulfonyl include, but are not particularly limited to, Ci_₆ straight-chain or branched-chain alkylsulfinyl groups substituted with 1 to 9, preferably 1 to 5, halogen atoms, such as fluoromethylsulfonyl ,

chloromethylsulfonyl, bromomethylsulfonyl, iodomethylsulfonyl , dichloromethylsulfonyl , trichloromethylsulfonyl ,

difluoromethylsulfonyl , trifluoromethylsul fonyl ,

chlorodifluoromethylsulfonyl , bromodifluoromethylsulfonyl , dichlorofluoromethylsulfonyl, 2,2, 2-trichloroethylsulfonyl,

2 , 2 , 2-trifluoroethylsulfonyl , pentafluoroethylsulfonyl, and the like.

Examples of <c ₆ alkylsulfinyl include, but are not particularly limited to, C_x_6 straight-chain or branched-chain alkylsulfinyl groups, such as methylsulfinyl , ethylsulfinyl , n-propylsulfinyl , isopropylsulfinyl , n-butylsulfinyl ,

isobutylsulfinyl , sec-butylsulfinyl , tert-butylsulfinyl , and the like.

Examples of Ci_₆ haloalkylsulfinyl include, but are not particularly limited to, Ci-6 straight-chain or branched-chain alkylsulfinyl substituted with 1 to 9, and preferably 1 to 5, halogen atoms, such as fluoromethylsulfinyl,

chloromethylsulfinyl, bromomethylsulfinyl, iodomethylsulfinyl , dichloromethylsulfinyl , trichloromethylsulfinyl ,

difluoromethylsulfinyl , trifluoromethylsulfinyl ,

chlorodifluoromethylsulfinyl , bromodifluoromethylsulfinyl, dichlorofluoromethylsulfinyl , 2,2,2-trichloroethylsulfinyl, 2,2,2-trifluoroethylsulfinyl, pentafluoroethylsulfinyl , and the like.

Examples of Ci-6 alkylthio include, but are not

particularly limited to, Ci-6 straight-chain or branched-chain alkylthio, such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio , sec-butylthio , tert- butylthio, and the like.

Examples of Ci-6 haloalkylthio include, but are not particularly limited to, Ci-6 straight-chain or branched-chain alkylthio substituted with 1 to 9, and preferably 1 to 5, halogen atoms, such as fluoromethylthio, chloromethylthio, bromomethylthio, iodomethylthio , dichloromethylthio, tri chloromethylthio, difluoromethylthio, trifluoromethylthio , chlorodifluoromethylthio , bromodifluoromethylthio,

dichlorofluoromethylthio, 2 , 2 , 2-trichloroethylthio, 2,2,2- trifluoroethylthio, pentafluoroethylthio , and the like.

Examples of C3-8 cycloalkylsulfonyl include, but are not particularly limited to, cyclopropylsulfonyl ,

cyclobutylsulfonyl , cyclopentylsulfonyl , cyclohexylsulfonyl , and the like.

Examples of C3-8 cycloalkylsulfinyl include, but are not particularly limited to, cyclopropylsulfinyl ,

cyclobutylsulfinyl , cyclopentylsulfinyl , cyclohexylsulfinyl , and the like.

Examples of C₃_₈ cycloalkylthio include, but are not particularly limited to, cyclopropylthio, cyclobutylthio, cyclopentylthio , cyclohexylthio, and the like.

Examples of C_{3 8} cycloalkyl Ci-6 alkylsulfonyl include, but are not particularly limited to, cyclopropylmethylsulfonyl , 2- cyclopropylethylsulfonyl, 3-cyclopropylpropylsulfonyl , cyclohexylmethylsulfonyl , and the like.

Examples of C ₈ cycloalkyl Ci-6 alkylsulfinyl include, but are not particularly limited to, cyclopropylmethylsulfinyl , 2- cyclopropylethylsulfinyl, 3-cyclopropylpropylsulfinyl, cyclohexylmethylsulfinyl , and the like.

Examples of C3-8 cycloalkyl Ci-s alkylthio include, but are not particularly limited to, cyclopropylmethylthio, 2- cyclopropylethylthio, 3-cyclopropylpropylthio,

cyclohexylmethylthio , and the like.

Examples of Ci-6 alkoxy Ci_₆ alkylthio include, but are not particularly limited to, alkoxyalkylthio in which C e

straight-chain or branched-chain alkylthio is substituted with Ci-6 straight-chain or branched-chain alkoxy, such as

methoxymethylthio, ethoxymethylthio, n-propoxymethylthio, isopropoxymethylthio, n-butoxymethylthio, sec- butoxymethylthio, tert-butoxymethylthio , 2-methoxyethylthio, and the like

Examples of C₂-6 alkenyloxy include, but are not

particularly limited to, vinyloxy, 1-propenyloxy ,

isopropenyloxy , allyloxy, 2-butenyloxy, 3-butenyloxy , 1- methylallyloxy, and the like.

Examples of C₂-6 haloalkenyloxy include, but are not particularly limited to, 2 , 2-dichlorovinyloxy , 2,2- dibromovinyloxy, 2 , 2-difluorovinyloxy, 3, 3-difluoro-2- allyloxy, 4 , -difluoro-3-butenyloxy, 4 , 4 , 4-trifluoro-2- butenyloxy, and the like.

Examples of C₂-6 alkynyloxy include, but are not ; particularly limited to, ethynyloxy, 2-propynyloxy, 1-methyl- 2-propynyloxy, 1 , l-dimethyl-2-propynyloxy , 1-butynyloxy , 2- butynyloxy, 3-butynyloxy , and the like.

Examples of C₂-6 haloalkynyloxy include, but are not particularly limited to, fluoroethynyloxy , bromoethynyloxy , chloroethynyloxy, iodoethynyloxy, 3, 3, 3-trifluoro-1- propynyloxy, and the like.

Examples of Ci_6 al kylsulfonyloxy include, but are not particularly limited to, Ci-e straight-chain or branched-chain alkylsulfonyl groups, such as methylsulfonyloxy,

ethylsulfonyloxy, n-propylsulfonyloxy, isopropylsulfonyloxy, n-butylsulfonyloxy, isobutylsulfonyloxy, sec-butylsulfonyloxy, tert-butylsulfonyloxy, and the like.

Examples of Ci-6 alkylsulfinyloxy include, but are not particularly limited to, Ci-6 straight-chain or branched-chain alkylsulfinyloxy groups, such as methylsulfinyloxy,

ethylsulfinyloxy, n-propylsulfinyloxy, isopropylsulfinyloxy, n-butylsulfinyloxy, isobutylsulfinyloxy, sec-butylsulfinyloxy, tert-butylsulfinyloxy, and the like.

Examples of substituted or unsubstituted amino include, but are not particularly limited to, amino, monoalkylamino, dialkylamino, monoacylamino , and the like. Examples of the alkyl include Ci_₆ alkyl mentioned above, and the like.

Examples of the acyl include Ci-6 alkylcarbonyl , C ₆

haloalkylcarbonyl , Ci-₆ al koxycarbonyl , C^₆ haloalkoxycarbonyl , arylcarbonyl , aryloxycarbonyl mentioned above, and the like.

Examples of aryl include, but are not particularly limited to, phenyl, 1-naphthyl, 2-naphthyl, and the like.

Examples of aryl Ci-e alkyl include, but are not

particularly limited to, benzyl, phenylethyl, phenyl-n-propyl , and the like. These aryl Ci-₆ alkyls can be further substituted at both the parts alkyl as well as aryl.

Examples of aryloxy include, but are not particularly limited to, phenoxy, 1-naphthyloxy, 2-naphthyloxy, and the like.

Examples of aryl Ci_6 alkoxy include, but are not

particularly limited to, benzyloxy, phenylethoxy, phenyl-n- propoxy, phenyl-n-butoxy, 1-naphthylmethoxy, 2- naphthylmethoxy, and like.

Examples of heteroaryloxy include, but are not

particularly limited to, pyridinyloxy, pyrimidinyloxy, pyrazolyloxy, and the like.

Examples of arylsulfonyl include, but are not

particularly limited to, phenylsulfonyl , 1-naphthylsulfonyl , 2-naphthylsulfonyl , and the like.

Examples of arylsulfinyl include, but are not

particularly limited to, phenylsulfinyl , 1-naphthylsulfinyl , 2-naphthylsulfinyl , and the like.

Examples of arylthio include, but are not particularly limited to, phenylthio, ; 1-naphthylthio, 2-naphthylthio , and the like.

Examples of arylsulfonyloxy include, but are not

particularly limited to, phenylsulfonyloxy, 1- naphthylsulfonyloxy, 2-naphthylsulfonyloxy, and the like.

Examples of arylsulfinyloxy include, but are not particularly limited to, phenylsulfinyloxy, 1- naphthylsulfinyloxy , 2-naphthylsulfinyloxy , and the like.

Examples of aryl Ci_6 alkylthio include, but are not particularly limited to, benzylthio, phenylethylthio, phenyl- n-propylthio, phenyl-n-butylthio, 1-naphthylmethylthio, 2- naphthylmethylthio, and the like.

Examples of arylcarbonyl include, but are not

particularly limited to, phenylcarbonyl , 1-naphthylcarbonyl , 2-naphthylcarbonyl , and the like.

Examples of aryloxycarbonyl include, but are not

particularly limited to, phenyloxycarbonyl , 1- naphthyloxycarbonyl , 2-naphthyloxycarbonyl , and the like.

Examples of heteroaryl include, but are not particularly limited to, thienyl, furyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl , pyrazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, tetrazinyl, indolyl, isoindolyl, indazolyl, quinazolinyl , carbazolyl, benzoxazolyl , benzisoxazolyl , benzothiazolyl , benzisothiazolyl ,

benzimidazolyl , quinolinyl, isoquinolinyl , pyridoindolyl, cinnolinyl, phthalazinyl , quinoxalinyl , purinyl,

phenothiazinylfuranyl , benzofuranyl , chromanyl, benzothienyl , and the like.

All the Aryls and Heteroaryls mentioned above may

optionally be further substituted. Examples of the number of substituents include, but are not particularly limited to, 1 to 20 (preferably 1 to 10, and more preferably 1 to 5).

Examples of a heterocyclic group include, but are not particularly limited to, thienyl, furyl, tetrahydrofuryl , dioxolanyl, dioxanyl, pyrrolyl, pyrrolinyl, pyrrolidinyl , oxazolyl, isoxazolyl, oxazolinyl, oxazolidinyl, isoxazolinyl , thiazolyl, isothiazolyl , thiazolinyl, thiazolidinyl ,

isothiazolinyl , pyrazolyl, pyrazolidinyl , imidazolyl,

imidazolinyl , imidazolidinyl , oxadiazolyl, oxadiazolinyl , thiadiazolinyl, triazolyl, triazolinyl, triazolidinyl , tetrazolyl, tetrazolinyl , pyridyl, dihydropyridyl ,

tetrahydropyridyl , piperidyl, oxazinyl, dihydroxazinyl , morpholino, thiazinyl, dihydrothiazinyl , thiamorpholino, pyridazinyl, dihydropyridazinyl , tetrahydropyridazinyl , hexahydropyridazinyl , oxadiazinyl, dihydrooxadiazinyl , tetrahydrooxadiazinyl , thiadiazolyl , thiadiazinyl ,

dihydrothiadiazinyl , tetrahydrothiadiazinyl , pyrimidinyl, dihydropyrimidinyl , tetrahydropyrimidinyl ,

hexahydropyrimidinyl , pyrazinyl, dihydropyrazinyl ,

tetrahydropyrazinyl , piperazinyl, triazinyl, dihydrotriazinyl , tetrahydrotriazinyl , hexahydrotriazinyl , tetrazinyl,

dihydrotetrazinyl , indolyl, indolinyl, isoindolyl, indazolyl, quinazolinyl , dihydroquinazolyl , tetrahydroquinazolyl , carbazolyl, benzoxazolyl , benzoxazolinyl, benzisoxazolyl , benzisoxazolinyl , benzothiazolyl, benzisothiazolyl , benzisothiazolinyl , benzimidazolyl , indazolinyl, quinolinyl, dihydroquinolinyl , tetrahydroquinolinyl , isoquinolinyl , dihydroisoquinolinyl , tetrahydroisoquinolinyl , pyridoindolyl , dihydrobenzoxazinyl , cinnolinyl, dihydrocinnolinyl ,

tetrahydrocinnolinyl , phthalazinyl , dihydrophthalazinyl , tetrahydrophthalazinyl, quinoxalinyl , dihydroquinoxalinyl, tetrahydroquinoxalinyl , purinyl, dihydrobenzotriazinyl , dihydrobenzotetrazinyl , phenothiazinylfuranyl , benzofuranyl , chromanyl, benzothienyl , and the like.

These heterocyclic groups include those substituted at any substitutable position with an oxo or thioketone group.

All the heterocyclics mentioned above may optionally be further substituted. Examples of the number of substituents include, but are not particularly limited to, 1 to 20

(preferably 1 to 10, and more preferably 1 to 5) .

Examples of "substituted" or "substituents" include: but are not particularly limited to, the halogen, nitro, cyano, hydroxyl, formyl, Ci_₆ alkyl, Ci_₆ haloalkyl, Ci_₆ alkoxy, C_x_₆ haloalkoxy, Ci-₆ alkoxy Ci_6 alkyl, Ci_₆ haloalkoxy Ci-₆ alkyl, C₃_ 8 cycloalkyl, C₃-₈ cycloalkyl Ci_₆ alkyl, Ci-₆ alkylcarbonyl , Ci_₆ haloalkylcarbonyl, Ci_6 alkoxycarbonyl , Ci-6 haloalkoxycarbonyl , arylcarbonyl , aryloxycarbonyl , Ci-₆ cyanoalkyl, Ci-6

cyanoalkoxy, C₂_₆ alkenyl, C₂ 6 haloalkenyl, C₂-6 alkynyl, C₂-6 haloalkynyl, Ci_₆ alkylsulfonyl , Ci_₆ haloalkylsulfonyl , Ci_₆ alkylsulfinyl , Ci_₆ haloalkylsulfinyl , Ci_₆ alkylthio, Ci^₆ haloalkylthio , C₃_₈ cycloalkylsulfonyl , C₃_₈ cycloalkylsulfinyl, C₃_₈ cycloalkylthio, C₃~₈ cycloalkyl Ci-₆ alkylsulfonyl, C₃-₈ cycloalkyl Ci_₆ alkylsulfinyl , C₃^₈ cycloalkyl Ci_₆ alkylthio, Ci- 6 alkoxy Ci_6 alkylsulfonyl , Ci_₆ alkoxy Ci-6 alkylsulfinyl, Ci_₆ alkoxy C ₆ alkylthio, C₂-6 alkenyloxy, C₂~₆ haloalkenyloxy, C₂-6 alkynyloxy, C₂-6 haloalkynyloxy, Ci_₆ alkylsulfonyloxy, Ci_₆ haloalkylsulfonyloxy, Ci-6 alkylsulfinyloxy, Ci_₆

haloalkylsulfinyloxy, OCN, SCN, SF₅, substituted or

unsubstituted amino, aryl, aryl C ₆ alkyl, aryloxy, aryl Ci_₆ alkoxy, arylsulfonyl , arylsulfinyl , arylthio, aryl Ci-6

alkylsulfonyl , aryl Ci_₆ alkylsulfinyl , aryl Ci_₆ alkylthio, heterocyclic, heterocyclic Ci~₆ alkyl, heterocyclic oxy, and the like.

The salts of the compounds represented by Formula (1) may be any type of salts as long as they are agriculturally acceptable. Examples of the salts include inorganic acid salts, such as a hydrochloride salt, a sulfate salt, a nitrate salt, and the like; organic acid salts such as an acetate salt, a methanesulfonic acid salt, and the like; alkali metal salts such as a sodium salt, a potassium salt, and the like; alkaline earth metal salts such as a magnesium salt, a calcium salt, and the like; quaternary ammonium salts such as

dimethylammonium, triethylammonium, and the like; and the like.

In the present invention, the N-oxide is a compound having atom constituting the ring in the heterocyclic group oxidized. A heterocyclic group which may constitute an N-oxide may, for example, be a condensed ring containing a pyridine ring, a condensed ring containing a pyrazine ring, a condensed ring containing a pyridazine ring or a condensed ring

containing a pyrimidine ring.

Among compounds (1) of the present invention, a

preferable compound is a compound in which R¹ is hydrogen, halogen or C_x_₆ alkyl, and a more preferable compound (1) is a compound in which R¹ is hydrogen or methyl.

Among compounds (1) of the present invention, a

preferable compound is a compound in which R² is hydrogen, halogen or Ci_6 alkyl, and a more preferable compound (1) is a compound in which R² is hydrogen.

Among compounds (1) of the present invention, a

preferable compound is a compound in which R³ is hydrogen, halogen or Ci-6 alkyl, and a more preferable compound (1) is a compound in which R³ is hydrogen.

Among compounds (1) of the present invention, a

preferable compound is a compound in which Y¹ is optionally substituted aryl or optionally substituted pyridyl, and a more preferable compound (1) is a compound in which Y¹ is

optionally substituted phenyl, optionally substituted 3- pyridyl or optionally substituted 4-pyridyl, and an especially preferable compound (1) is a compound in which Y¹ is optionally substituted 3-pyridyl.

Among compounds (1) of the present invention, a

preferable compound is a compound in which Y² is optionally substituted aryl or optionally substituted pyridyl and a more preferable compound (1) is a compound in which Y² is

optionally substituted phenyl.

Among compounds (1) of the present invention, a

preferable compound is a compound in which Q is cyano .

Among compounds (1) of the present invention, a

preferable compound is a compound in which R⁴, R⁵, R⁶, R⁷ and R⁸ are identical or different and each is hydrogen, halogen, Ci-6 alkyl, Ci_₆ haloalkyl, Ci_₆ alkoxy or Ci_6 haloalkoxy, and a more preferable compound (1) is a compound in which R⁴, R⁵, R⁶, R⁷ and R⁸ are identical or different and each is hydrogen, fluorine, chlorine, bromine, tert-butyl, trifluoromethyl, methoxy or trifluoromethoxy .

Among compounds (1) of the present invention, a

preferable compound is a compound m which R% R , R¹ , R^x% R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷;. R¹⁸, R¹⁹ and R²⁰ are identical or

different and each is hydrogen or halogen, and a more

preferable compound (1) is a compound in which R⁹, R¹⁰, R¹¹,

R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹ and R²⁰ are hydrogen or chlorine .

Among compounds (1) of the present invention, a preferable compound is a compound in which R²¹, R²², R²³, R²⁴ and R²⁵ are identical or different and each is hydrogen, halogen, nitro, cyano, optionally substituted amino, Ci-6 alkyl, Ci_₆ haloalkyl, Ci-₆ alkoxy, Ci-₆ haloalkoxy or optionally

substituted aryl, and a more preferable compound (1) is a compound in which R

are identical or different and each is hydrogen, fluorine, chlorine, bromine, nitro, cyano, amino, methyl, trifluoromethyl , methoxy,

trifluoromethoxy or phenyl.

Among compounds (1) of the present invention, a

preferable compound is a compound in which R²⁶, R²⁷, R²⁸, R²⁹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵, R³⁶ and R³⁷ are identical or

different and each is hydrogen or halogen, and a more

preferable compound (1) is a compound in which R , R , R , R²⁹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵, R³⁶ and R³⁷ is hydrogen.

Of these, a more preferable compound of the present invention is a compound or a salt or an N-oxide thereof in which

R¹ is hydrogen, halogen, or C ₆ alkyl;

R²; is hydrogen, halogen, or Ci_₆ alkyl;

R³ is hydrogen, halogen, or Ci-₆ alkyl;

Y¹ is optionally substituted aryl or optionally substituted pyridyl ;

Y² is optionally substituted aryl or optionally substituted pyridyl ; Q is cyano.

A more particularly preferable compound of the present invention is a compound or a salt or an N-oxide thereof in which

R¹ is hydrogen or methyl;

R² is hydrogen;

R³ is hydrogen;

Y¹ is optionally substituted phenyl, optionally substituted 3- pyridyl or optionally substituted 4-pyridyl;

Y² is optionally substituted phenyl;

Q is cyano.

A especially particularly preferable compound of the present invention is a compound or a salt or an N-oxide thereof in which

R¹ is hydrogen or methyl;

R² is hydrogen;

R³ is hydrogen;

Y¹ is optionally substituted 3-pyridyl;

Y² is optionally substituted phenyl;

Q is cyano.

The invention also provides a process for preparing a dithiolane or a salt or an N-oxide thereof represented by the Formula ( 1 ) :

wherein R¹, R², R³, Y¹, Y² and Q are as defined above.

The dithiolane compound represented by Formula (1) of the present invention can be readily prepared according to

following reaction scheme 1, but is not limited to these methods .

The dithiolane compound represented by Formula (1) can be prepared by the reaction of a compound (2) with a compound (3) and carbon disulfide in the presence of a base and a solvent as mentioned in reaction scheme 1.

Reaction scheme 1

(2) (3) (1)

Wherein, R¹, R², R³, Y¹, Y² and Q are as defined above. While, Ά and B are identical or different and each represents a

suitable leaving group such as chlorine, bromine, and iodine; substituted or unsubst ituted Ci-₆ alkyl sulfonate; and

substituted or unsubst ituted aryl sulfonate.

The amount of the compound (3) to be used is usually 0.5 to 5 mol, preferably 1 to 2 mol, per 1 mol of the compound (2) .

The amount of the carbon disulfide to be used is usually 2 to 10 mol, preferably 1 to 2 mol, per 1 mol of the compound (2) .

The reaction is carried out in the presence of a suitable base. As the base, a conventionally known base can widely be used, and examples of the bases include: alkali metal

carbonates such as sodium carbonate, potassium carbonate, cesium carbonate, potassium bicarbonate, sodium bicarbonate, and the like; alkali metal hydroxides such as sodium

hydroxide, potassium hydroxide, and the like; alkali metal hydrides such as sodium hydride and potassium hydride, and the like; alkali metal hydrides such as sodium hydride and

potassium hydride, and the like; alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, and the like; organic bases such as pyridine, triethylamine, diethylamine , dimethylamine , methylamine, imidazole,

benzimidazole , diisopropylethylamine , 4 -dimethylaminopyridine , piperidine, and the like, preferably sodium hydroxide,

potassium hydroxide, sodium hydride, potassium hydride sodium methoxide, sodium ethoxide and potassium tert-butoxide. Any separate one of these bases or a combination of two cor more types thereof is used.

In the case, when organic base is used, it can be used in large excess to serve as a solvent.

The amount of the base to be used is usually 2 to 5 mol, preferably 2 to 3 mol, per 1 mol of the compound (2) . The aforementioned reaction is performed in an

appropriate solvent or without any solvent. When the

aforementioned reaction is carried out in the solvent, no limitations are placed on the solvent as long as the solvent is inactive with respect to the aforementioned reaction.

Examples of such a solvent include: fatty acid or alicyclic hydrocarbon-based solvents such as n-hexane, cyclohexane, n-heptane, and the like; aromatic hydrocarbon- based solvents such as benzene, chlorobenzene , toluene, xylene, and the like; halogenated hydrocarbon-based solvents such as methylene chloride, 1, 2-dichloroethane, chloroform, and carbon tetrachloride, and the like; ether-based solvents such as diethyl ether, tetrahydrofuran (THF) , 1,4-dioxane, dimethoxyethane , and the like; esters solvents such as methyl acetate, ethyl acetate, and the like; acetonitrile ; amide- based solvents such as , N-dimethylformamide (DMF), N,N- dimethylacetoamide , N-methyl-2-pyrol idone, and the like;

sulfoxide-based solvents such as dimethyl sulfoxide (DMSO) , sulforane and the like; H₂0; acetic acid, preferably, DMSO, DMF, toluene and THF. Any one of these solvents can be used alone or a combination of two or more types thereof can be used when necessary.

The amount of the solvent to be used is usually 1 to 20 liter, preferably 1 to 10 liters, per 1 mol of the compound (2) . The reaction is usually done at a temperature from -10°C to boiling point of the solvent. The reaction time is usually in the range of 0.25 hour to 24 hours or more depending on the completion of the reaction.

The compound (2) used in this step can be produced according to a known method (for example, the method described in WO2007/045989, Synlett (15), 2223-2227 (2011) and Molecular Diversity 18(2), 307-322 (2014)).

The compound (3) used in this step can be produced according to a known method (for example, the method described in WO2006/110804, WO2015/003991 , WO2015/11194 and

O2015/162271) .

The compound represented by Formula (1) obtained by the method shown in Scheme 1 is easily isolated from a reaction mixture and can be purified by use of typical isolation means and purification means, for example, filtration, solvent extraction, distillation, recrystallization, column

chromatography, etc.

Although a form used for the present compound may be the present compound as itself, the present compound is usually prepared by mixing the present compound with solid carriers, liquid carriers, gas carriers, surfactants and the others, and if necessary, adding stickers, dispersers and stabilizers, to formulate into wettable powders, water dispersible granules, flowables, granules, dry flowables, emulsifiable concentrates, aqueous solutions, oil solutions, smoking agents, aerosols, microcapsules and the others. In these formulations, the present compound is contained in a range of usually 0.1 to 99%, preferably 0.2 to 90% by weight.

Examples of the solid carriers include clays (for

example, kaolin, diatomaceous earth, synthetic hydrated silicon dioxide, Fubasami clay, bentonite and acid clay) , talcs or the other inorganic minerals (for example, sericite, quartz powder, sulfur powder, activated charcoal, calcium carbonate and hydrated silica) in the form of fine powders or particulates, and examples of the liquid carries include water, alcohols (for example, methanol and ethanol), ketones (for example, acetone and methyl ethyl ketone), aromatic hydrocarbons (for example, benzene, toluene, xylene,

ethylbenzene and methyl naphthalene), aliphatic hydrocarbons (for example, n-hexane, cyclohexane and kerosene), esters (for example, ethyl acetate and butyl acetate), nitriles (for example, acetonitrile and isobutyronitrile), ethers (for

; example, dioxane and diisopropyl ether), acid amides (for example, DMF and dimethylacetamide ) , halogenated hydrocarbons (for example, dichloroethane trichloroethylene and carbon tetrachloride) and the others.

Examples of the surfactants include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylenated compounds thereof, polyethylene glycol ethers, polyol esters and sugar alcohol derivatives.

Examples of other auxiliary agents for formulation include stickers, dispersers and stabilizers, specifically casein, gelatin, polysaccharides (for example, starch, gum arabic, cellulose derivatives and alginic acid) , lignin derivatives, bentonite, sugars, water-soluble synthetic polymers (for example, polyvinyl alcohol, polyvinyl

pyrrolidone and polyacrylic acids), PAP (acidic isopropyl phosphate) , BHT (2, 6-di-tert -butyl-4 -methylphenol ) , BHA (a mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4- methoxyphenol ) , vegetable oils, mineral oils, fatty acids or fatty acid esters thereof and the others.

The method for applying the present compound is not particularly limited, as far as the applying form is a form by which the present compound may be applied substantially, and includes, for example, an application to plants such as a foliage application; an application to area for cultivating plants such as a submerged treatment; and an application to soil such as seed disinfection.

The application dose varies depending on weather

conditions, dosage forms, timing of application, methods of application, areas to be applied, target diseases and target crops etc., but is in the range of usually from 1 to 500 g, and preferably from 2 to 200 g per 1,000 m² of the area to be applied. The emulsifiable concentrate, the wettable powder or the suspension concentrate, etc., is usually applied by diluting it with water. In this case, the concentration of the present compound after dilution is in the range of usually 0.0005 to 2% by weight, and preferably 0.005 to 1% by weight. The dust formulation or the granular formulation etc., is usually applied, as itself without diluting it. In the application to seeds, the amount of the present compound is in the range of usually from 0.001 to 100 g, and preferably from 0.01 to 50 g per 1 kg of the seeds.

Herein, examples of the place where the pests live include paddy fields, fields, tea gardens, orchards, non- agricultural lands, houses, nursery trays, nursery boxes, nursery soils and nursery bed.

Also, in another embodiment, for example, the present compound can be administered to the inside (inside of the body) or the outside (body surface) of the below-mentioned vertebrate to exterminate systemically or unsystemically living things or parasites which are parasitic on the

vertebrate. Examples of a method of the internal medication include an oral administration, an anal administration, a transplantation, an administration via injection

subcutaneously, intramuscularly or intravenously. Examples of a method of outside medication include a transdermal

administration. Also, the present compound can be ingested to a livestock animal so as to exterminate sanitary insects which occur in the excrement of the animal.

When the present compound is applied to the animals such as the livestock animal and pets on which pests are parasitic, the dose varies depending on the administration method etc., but it is desirable in general to administer the present compound so that a dose of the active ingredient (the present compound or salts thereof) is in the range of generally from 0.1 mg to 2,000 mg and preferably 0.5 mg to 1,000 mg per 1 kg of body weight of the animal.

The present compound can be used as an agent for

controlling plant disease in agricultural lands such as fields, paddy fields, lawns, orchards. The compound of the present invention can control diseases occurred in the

agricultural lands or the others for cultivating the following ' ' plant ' ' .

Crops: corn, rice, wheat, barley, rye, oat, sorghum, cotton, soybean, peanut, buckwheat, beet, rapeseed, sunflower, sugar cane, tobacco, and the others; Vegetables: solanaceous vegetables (for example, eggplant, tomato, pimento, pepper and potato), cucurbitaceous vegetables (for example, cucumber, pumpkin, zucchini, water melon and melon) , cruciferous

vegetables (for example, Japanese radish, white turnip, horseradish, kohlrabi, Chinese cabbage, cabbage, leaf mustard, broccoli, cauliflower), asteraceous vegetables (for example, burdock, crown daisy, artichoke and lettuce) , liliaceous vegetables (for example, green onion, onion, garlic and asparagus), ammiaceous vegetables (for example, carrot, parsley, celery and parsnip), chenopodiaceous vegetables (for example, spinach and Swiss chard), lamiaceous vegetables (for example, Perilla frutescens, mint and basil), strawberry, sweet potato, Dioscorea japonica, colocasia and the others; Flowers: Ornamental foliage plants: Fruits: pomaceous fruits (for example, apple, pear, Japanese pear, Chinese quince and quince), stone fruits (for example, peach, plum, nectarine, Prunus mume, cherry fruit, apricot and prune), citrus fruits (for example, Citrus unshiu, orange, lemon, lime and

grapefruit), nuts (for example, chestnut, walnut, hazelnut, almond, pistachio, cashew nut and macadamia nut), berry fruits (for example, blueberry, cranberry, blackberry and raspberry), grape, kaki persimmon, olive, Japanese plum, banana, coffee, date palm, coconut, and the others; Trees other than fruit trees: tea, mulberry, flowering plant, roadside trees (for example, ash, birch, dogwood, Eucalyptus, Ginkgo biloba, lilac, maple, Quercus, poplar, Judas tree, Liquidambar

formosana, plane tree, zelkova, Japanese arborvitae, fir wood, hemlock, juniper, Pinus, Picea, and Taxus cuspidata); and the others.

The above-mentioned "plant" includes genetically modified crops . The pests on which the present compound has a control efficacy include plant pathogens such as filamentous fungus, as well as harmful arthropods such as harmful insects and harmful mites, and nemathelminth such as nematodes, and specifically include the following examples, but are not limited thereto.

Rice diseases: blast (Magnaporthe grisea) , brown spot (Cochliobolus miyabeanus), sheath blight (Rhizoctonia solani) , bakanae disease (Gibberella fujikuroi), and downy mildew

(Sclerophthora macrospora) ;

Wheat diseases: powdery mildew (Erysiphe graminis), fusarium blight (Fusarium graminearum, F. avenaceum, F.

culmorum, Microdochium nivale) , rust (Puccinia striiformis, P. graminis, P. recondita) , snow mould (Micronectriella nivale), typhulasnow blight (Typhula sp.), loose smut (Ustilago

tritici), stinking smut (Tilletia caries, T. controversa) , eyespot (Pseudocercosporella herpotrichoides), leaf blotch (Septoria tritici), glume blotch ( Stagonospora nodorum) , tan spot (Pyrenophora tritici-repentis ) , rhizoctonia seeding blight (Rhizoctonia solani), and take all disease

( Gaeumannomyces graminis);

Barley diseases: powdery mildew (Erysiphe graminis), fusarium blight (Fusarium graminearum, F. avenaceum, F.

culmorum, Microdochium nivale), rust (Puccinia striiformis, P. graminis, P. hordei), loose smut (Ustilago nuda), scald ( Rhynchosporium secalis), net blotch (Pyrenophora teres), spot blotch (Cochliobolus sativus), leaf stripe (Pyrenophora graminea) , Ramularia disease (Ramularia collo-cygni ) , and rhizoctonia seeding blight (Rhizoctonia solani);

Corn diseases: rust (Puccinia sorghi), southern rust

(Puccinia polysora) , northern leaf blight ( Setosphaeria turcica), southern leaf blight (Cochliobolus heterostrophus ) , anthracnose (Colletotrichum graminicola), gray leaf spot

(Cercospora zeae-maydis ) , eyespot (Kabatiella zeae), and phaeosphaeria leaf spot ( Phaeosphaeria maydis);

Cotton diseases: anthracnose (Colletotrichum gossypii), grey mildew (Ramularia areola) , alternaria leaf spot

(Alternaria macrospora, A. gossypii);

Coffee diseases: rust (Hemileia vastatrix) ;

Rape seed diseases: sclerotinia rot (Sclerotinia

sclerotiorum) , black spot (Alternaria brassicae), and black leg (Phoma lingam) ;

Citrus diseases: melanose (Diaporthe citri), scab

(Elsinoe fawcettii), and fruit rot (Penicillium digitatum, P. italicum) ;

Apple diseases: blossom blight (Monilinia mali), canker (Valsa ceratosperma) , powdery mildew (Podosphaera

leucotricha) , alternaria leaf spot (Alternaria alternata apple pathotype), scab (Venturia inaequalis) , and bitter rot

(Colletotrichum acutatum) ; Pear diseases: scab (Venturia nashicola, V. pirina) , black spot (Alternaria alternate Japanese pear pathotype) and rust (Gymnosporangium haraeanum) ;

Peach diseases: brown rot (Monilinia fructicola), scab (Cladosporium carpophilum) and Phomopsis rot (Phomopsis s . ) ;

Grapes diseases: anthracnose (Elsinoe ampelina) , ripe rot (Glomerella cingulata) , powdery mildew (Uncinula necator) , rust (Phakopsora ampelopsidis ) , black rot (Guignardia

bidwellii) , and downy mildew (Plasmopara viticola) ;

Diseases of Japanese persimmon: anthracnose (Gloeosporium kaki) and leaf spot (Cercospora kaki, Mycosphaerella nawae) ;

Diseases of gourd family: anthracnose (Colletotrichum lagenarium) , powdery mildew ( Sphaerotheca fuliginea) , gummy stem blight (Didymella bryoniae) , target spot (Corynespora cassiicola), fusarium wilt (Fusarium oxysporum) , downy mildew ( Pseudoperonospora cubensis), phytophthora rot ( Phytophthora sp.) and damping-off (Pythium sp.) ;

Tomato diseases: early blight (Alternaria solani), leaf mold (Cladosporium fulvum) , leaf mold ( Pseudocercospora fuligena) , and late blight (Phytophthora infestans) ;

Eggplant disease: brown spot (Phomopsis vexans) and powdery mildew (Erysiphe cichoracearum) ;

Diseases of Cruciferous Vegetables: alternaria leaf spot (Alternaria japonica), white spot (Cercosporella brassicae) , clubroot (Plasmodiophora parasitica), downy mildew (Peronospora parasitica);

Welsh onion diseases: rust (Puccinia allii);

Soybean diseases: purple stain (Cercospora kikuchii) , sphaceloma scad (Elsinoe glycines), pod and stem blight

(Diaporthe phaseolorum var. sojae), rust (phakopsora

pachyrhizi), target spot (Corynespora cassiicola) , anthracnose (Colletotrichum glycines, C. truncatum) , Rhizoctonia aerial blight (Rhizoctonia solani) , septoria brown spot (Septoria glycines) and frog eye leaf spot (Cercospora sojina);

Kidney bean diseases: anthracnose (Colletotrichum

lindemuthianum) ;

Peanut diseases: early leaf spot (Cercospora personata) , late leaf spot (Cercospora arachidicola ) and southern blight (Sclerotium rolfsii);

Garden pea diseases: powdery mildew (Erysiphe pisi);

Potato diseases: early blight (Alternaria solani), late blight ( Phytophthora infestans), and verticillium wilt

(verticillium albo-atrum, V. dahliae, V. nigrescens ) ;

Strawberry diseases: powdery mildew ( Sphaerotheca

humuli ) ;

Tea diseases: net blister blight (Exobasidium

reticulatum) , white scab (Elsinoe leucospila), gray blight ( Pestalotiopsis sp . ) and anthracnose (Colletotrichum theae- sinensis ) ;

Tobacco diseases: brown spot (Alternaria longipes), powdery mildew (Erysiphe cichoracearum) , anthracnose

(Colletotrichum tabacum), downy mildew (Peronospora tabacina) , and black shank (Phytophthora nicotianae);

Sugar beet diseases: cercospora leaf spot (Cercospora beticola) , leaf blight (Thanatephorus cucumeris) , root rot (Thanatephorus cucumeris) and aphanomyces root rot

(Aphanomyces cochlioides ) ;

Rose diseases: black spot (Diplocarpon rosae) and powdery mildew ( Sphaerotheca pannosa) ;

Diseases of Chrysanthemum: leaf blight (Septoria

chrysanthemi-indici ) and white rust (Puccinia horiana) ;

Onion diseases: botrytis leaf blight (Botrytis cinerea, B. byssoidea, B. squamosa), gray-mold neck rot (Botrytis allii), and small sclerotial rot (Botrytis squamosa);

Various crops diseases: gray mold (Botrytis cinerea), and sclerotinia rot (Sclerotinia sclerotiorum) ;

Diseases of Japanese radish: alternaria leaf spot

(Alternaria brassicicola) ;

Turfgrass diseases: dollar spot (Sclerotinia

homoeocarpa) , brown patch and large patch ( Rhi;zoctonia

solani ) ; and

Banana diseases: Sigatoka disease (Mycosphaerella

fijiensis, Mycosphaerella musicola).

Hemiptera: Delphacidae (for example, Laodelphax

striatellus, Nilaparvata lugens, or Sogatella furcifera) ; Deltocephalinae (for example, Nephotettix cincticeps, or

Nephotettix virescens) ; Aphididae (for example, Aphis

gossypii, Myzus persicae, Brevicoryne brassicae, Macrosiphum euphorbiae, Aulacorthum solani, Rhopalosiphum padi, Toxoptera citricidus ) ; Pentatomidae (for example, Nezara antennata,

Riptortus clavatus, Leptocorisa chinensis, Eysarcoris parvus, Halyomorpha mista, or Lygus lineolaris ) ; Aleyrodidae (for example, Trialeurodes vaporariorum, or Bemisia argentifolii ) ; Coccoidea (for example, Aonidiella aurantii, Comstockaspis perniciosa, Unaspis citri, Ceroplastes rubens, or Icerya purchasi); Tingidae, Psyllidae; Bed bugs (Cimex lectularius) and the others.

Lepidoptera: Pyralidae (for example, Chilo suppressalis , Tryporyza incertulas, Cnaphalocrocis medinalis, Notarcha derogata, Plodia interpunctella , Ostrinia furnacalis, Hellula undalis, Pediasia teterrellus) , Noctuidae (for example,

Spodoptera litura, Spodoptera exigua, Pseudaletia separata, Mamestra brassicae, Agrotis ipsilon, Plusia nigrisigna,

Trichoplusia spp., Heliothis spp., or Helicoverpa spp.);

Pieridae (for example, Pieri;s rapae) , Tortricidae (for

example, Adoxophyes spp., Grapholita molesta, Cydia pomonella, Leguminivora glycinivorella , Matsumuraeses azukivora,

Adoxophyes orana fasciata, Adoxophyes sp . , Homona magnanima, Archips fuscocupreanus , Cydia pomonella); Gracillariidae (for example, Caloptilia theivora, Phyllonorycter ringoniella) ; Carposinidae (for example, Carposina niponensis ) ; Lyonetiidae (for example, Lyonetia spp.); Lymantriidae (for example, Lymantria spp., or Euproctis spp.); Yponomeutidae (for example, Plutella xylostella); Gelechiidae (for example, Pectinophora gossypiella or Phthorimaea operculella) ;

Arctiidae (for example, Hyphantria cunea) ; Tineidae (for example, Tinea translucens, or Tineola bisselliella); and the others ;

Thysanoptera : Thysanoptera (for example, Frankliniella occidentalis , Thrips palmi, Scirtothrips dorsalis, Thrips tabaci, Frankliniella intonsa, Frankliniella fusca) ;

Diptera: Musca domestica, Culex pipiens pallens, Tabanus trigonus, Hylemya antiqua, Hylemya platura, Anopheles sinensis, Agromyza oryzae, Hydrellia griseola, Chlorops oryzae, Dacus cucurbitae, Ceratitis capitata, Liriomyza trifolii, and the others;

Coleoptera: Epilachna vigintioctopunctata , Aulacophora femoralis, Phyllotreta striolata, Oulema oryzae, Echinocnemus squameus, Lissorhoptrus oryzophilus, Anthonomus grandis, Callosobruchus chinensis, Sphenophorus venatus, Popillia japonica, Anomala cuprea, Diabrotica spp., Leptinotarsa decemlineata , Agriotes spp., Lasioderma serricorne, Anthrenus verbasci, Tribolium castaneum, Lyctus brunneus, Anoplophora malasiaca, Tomicus piniperda, and the others;

Orthoptera: Locusta migratoria, Gryllotalpa africana, Oxya yezoensis, Oxya japonica, and the others;

Hymenoptera: Athalia rosae, Acromyrmex spp., Solenopsis spp., and the others;

Nematodes: Aphelenchoides besseyi, Nothotylenchus acris, Heterodera glycines, Meloidogyne incognita, Pratylenchus , Nacobbus aberrans, and the others;

Blattariae: Blattella germanica, Periplaneta fuliginosa, Periplaneta americana, Periplaneta brunnea, Blatta orientalis, and the others;

Acarina: Tetranychidae (for example, Tetranychus urticae,

Panonychus citri, or Oligonychus spp.); Eriophyidae (for example, Aculops pelekassi); Tarsonemidae (for example,

Polyphagotarsonemus latus); Tenuipalpidae ; Tuckerellidae

Acaridae (for example, Tyrophagus putrescentiae) ;

Pyroglyphidae (for example, Dermatophagoides farinae, or

Dermatophagoides pteronyssinus ) ; Cheyletidae (for example, Cheyletus eruditus, Cheyletus malaccensis, or Cheyletus moorei); Dermanyssidae ; and the others.

The formulation comprising the present compound or salts thereof can also be used in the field relating to a treatment of livestock diseases or livestock industry, and for example, can exterminate the living things or parasites which are parasitic on the inside and/or the outside of a vertebrate such as human being, cow, sheep, pig, poultry, dog, cat and fish, so as to maintain public health. Examples of the pests include Ixodes spp . (for example, Ixodes scapularis), Boophilus spp. (for example, Boophilus microplus), Amblyomma spp., Hyalomma spp., Rhipicephalus spp.

(for example, Rhipicephalus sanguineus), Haemaphysalis spp.

(for example, Haemaphysalis longicornis), dermacentor spp., Ornithodoros spp. (for example, Ornithodoros moubata),

Dermanyssus gallinae, Ornithonyssus sylviarum, Sarcoptes spp.

(for example, Sarcoptes scabiei) , Psoroptes spp., Chorioptes spp., Demodex spp., Eutrombicula spp., Ades spp. (for example Aedes albopictus), Anopheles spp., Culex spp., Culicoides spp., Musca spp., Hypoderma spp., Gasterophilus spp.,

Haematobia spp., Tabanus spp., Simulium spp., Triatoma spp., Phthiraptera (for example, Damalinia spp.), Linognathus spp., Haematopinus spp., Ctenocephalides spp. (for example,

Ctenocephalides felis) Xenopsylla spp., monomorium pharaonis and nematodes, hairworm (for example, Nippostrongylus

brasiliensis , Trichostrongylus axei, Trichostrongylus

colubriformis ) , Trichinella spp. (for example, Trichinella spiralis), Haemonchus contortus, Nematodirus spp. (for example, Nematodirus battus), Ostertagia circumcincta ,

Cooperia spp., Hymenolepis nana, and the others.

The dithiolane (1) of the invention is used, for example as active ingredient for a fungicide.

The dithiolane (1) of the invention can be used by being made into the desirable form such as oil, emulsion, wettable powder, flowable preparation, granules, powder, aerosol, fumigant or the like. In this case, the content of the dithiolane (1) of the invention is not limited and can be suitably selected from a wide range according to various conditions such as the form of preparation, kind of disease to be treated, kind of plant, severity of disease, place of application, time of application, method of application, chemicals to be used in combination (insecticide, nematicide, acaricide, fungicide, herbicide, plant growth control agent, synergist, soil conditioner, etc.), amount and kind of fertilizer and so on. The content is usually about 0.01 to about 95% by weight, based on the total amount of the

fungicidal preparation.

A fungicidal preparation containing the dithiolane (1) of the invention as the active ingredient can be produced

according to known processes. For example, the dithiolane (1) of the invention may be mixed with a carrier such as a solid carrier, a liquid carrier, a gaseous carrier or the like.

Optionally a surfactant and other adjuvants for

preparation may be added.

Useful carriers can be any of known ones which are usually used in this field.

Examples of useful solid carriers are fine or granules of clays (kaolin clay, diatomaceous earth, synthetic hydrated silicon dioxide, bentonite, fubasami clay, acid clay, and the like), talcs, ceramics, other inorganic minerals, cerite, quartz, sulfur, activated carbon, calcium carbonate, hydrated silica, etc.), and so on.

Useful liquid carriers are, for example, water, alcohols (such as methanol, ethanol, etc.), ketones (such as acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (such as benzene, toluene, xylene, ethylbenzene , methylnaphthalene , etc.), aliphatic hydrocarbons (such as hexane, cyclohexane, kerosene, light oil, etc.), esters (such as ethyl acetate, butyl acetate, etc.), nitriles (such as acetonitrile, isobutyronitrile, etc.), ethers (such as diisopropyl ether, dioxane, etc.), acid amides (such as N, -dimethylformamide, N , N-dimethylacetamide , etc.), haloqenated hydrocarbons (such as dichloromethane , trichloroethane , carbon tetrachloride, etc.), dimethylsulfoxide, soybean oil, cotton seed oil, vegetable oils and so on.

Examples of useful gaseous carriers (propellants ) are butane gas, LPG (liquefied petroleum gas), dimethyl ether, carbon dioxide, etc.

Examples of useful surfactants are alkyl ester sulfates, alkyl sulfonates, alkylarylsulfonates, alkyl aryl ethers, polyoxyethylenated products thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol compounds, etc . Examples of useful adjuvants for preparation are fixing agents such as casein, gelatin, polysaccharides (starch powder, gum arabic, cellulose compound, alginic acid, etc.)_? lignin compounds, bentonite, saccharides, synthetic water- soluble polymers (polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, etc.), and the like; stabilizers such as PAP (acidic isopropyl phosphate), BBH (2, 6-di-tert-butyl-4- methylphenol ) , BHA (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol ) , vegetable oils, mineral oils, fatty acids, esters thereof, and the like.

The fungicidal preparation of the invention thus obtained can be used as it is or as diluted with water. The preparation may be prepared by being mixed with any of insecticides, nematicides, acaricides, fungicides, herbicides, plant growth control agents, synergists, soil conditioners, etc. The preparation of the invention may be applied simultaneously with other preparations.

When the preparation of the invention is used as a fungicide for use in agriculture and horticulture, the amount of the preparation of the invention is not limited and can be suitably selected from a wide range according to various conditions such as the concentration of active ingredient, the form of preparation, kind of disease to be treated, kind of plant, severity of disease or mite, time for application, method of application, chemicals to be used in combination (insecticide, nematicide, miticide, fungicide, herbicide, plant growth control agent, synergist, soil conditioner, etc.), amount and kind of a fertilizer and so on. The amount is usually about 0.001 to about 100 g per 100 m² of the area. When an emulsion, wettable powder, flowable preparation or the like diluted with water is used, the concentration of the fungicidal or miticidal preparation is about 0.1 to about 1000 ppm, preferably about 1 to 500 ppm. The granules, particles or the like are applied as such without dilution.

The compound of the invention is characterized by having an excellent fungicidal activity and a broad spectrum of activity. The compound can be used for control of plant diseases ascribed to pathogenic fungi and resistant pathogenic fungi. Examples of such pathogenic fungi include those that cause or are resistant to fungicides to treat rice plant blast, rice plant sheath blight, grey mould on tomato, and the like, apple powdery mildew, apple alternaria blotch, persimmon powdery mildew, grape powdery mildew, barley powdery mildew, wheat powdery mildew, cucumber powdery mildew, cucumber gray mold, tomato late blight, potato blight, and the like.

Examples

The invention will be described in more details with reference to Preparation examples, Formulation examples and Test examples. The present invention describes in more details with reference to the following Reference examples, Production examples, Formulation example and Test examples. However, the present invention is not limited to these examples. In addition, alterations can be made within the scope that does not depart from the scope of the present invention.

Reference example 1

Preparation of 2-bromo-l- (2-chlorophenyl) ethanone

To a cooled solution of 1- (2-chlorophenyl) ethanone (10.00 g, 64.51 mmol) in diethyl ether (35 ml) was slowly added bromine (3.32 mL, 64.51 mmol) at 0°C. The resulting reaction mixture was then stirred at 0°C for 3 hrs. After distillation of all volatiles under reduced pressure, the residue was quenched by aqueous solution of sodium thiosulfate and

extracted with diethyl ether (3 x 20 ml) . The combined organic layer was washed with distilled water followed by brine solution, dried over sodium sulfate, filtered and concentrated under reduced pressure to get 14.90 g of crude product as a light brown liquid. It was then used in the next step without further purification.

^XH N R (CDC1₃, 400 MHz) δ: 7.57-7.55 (m, 1H), 7.48-7.44 (m, 2H) , 7.38-7.36 (m, 1H) , 4.52 (s, 2H) . Reference example 2 Preparation of 2-bromo-l- ( 2-chIorophenyl ) ethanol

To a cooled solution of 2-bromo-l- ( 2- chlorophenyl ) ethanone (10.00 g, 42.91 mmol) in methanol (40 ml), sodium borohydride (1.63 g, 42.91 mmol) was portion-wise added at 0°C. The resulting reaction mixture was then stirred at room temperature for 1 hr. After distillation of all volatiles under reduced pressure, the residue was quenched by distilled water (70 ml) and extracted with ethyl acetate (3 x 20 ml) . The combined organic layer was washed with distilled water followed by brine solution, dried over sodium sulfate, filtered and concentrated under reduced pressure to get 9.90 g of crude product as a colorless liquid. It was then used in the next step without further purification.

^XH NMR (CDC1₃, 400 MHz) δ: 7.64-7.62 (m, 1H), 7.37-7.33 (m, 1H) , 7.28-7.27 (m, 1H) , 7.24-7.22 (m, 1H) , 5.33-5.30 (m, 1H) , 3.81-3.78 (m, 1H) , 3.47-3.42 (m, 1H) , 2.71-2.70 (m, 1H) .

Reference example 3

Preparation of 2-bromo-l- (2-chlorophenyl ) ethyl

methanesulfonate

To a cooled solution of 2-bromo-l- (2-chlorophenyl ) ethanol (9.90 g, 41.94 mmol) in tetrahydrofuran (35 ml) was slowly added triethylamine (6.35 g, 62.92 mmol) followed by

methanesulfonyl chloride (4.82 g, 41.94 mmol) at 0°C. The resulting reaction mixture was then stirred at 0°C for 2 hrs . After distillation of all volatiles under reduced pressure, the residue was quenched by distilled water (70 ml) and extracted with ethyl acetate (4 x 20 ml) . The combined organic layer was washed with distilled water followed by brine solution, dried over sodium sulfate, filtered and concentrated under reduced pressure to get 12.40 g of crude product as a white solid. It was then used in the next step without further purification .

¹H NMR (CDC1₃, 400 MHz) δ: 7.59-7.54 (m, 1H), 7.42-7.35 (m, 2H) , 7.24-7.22 (m, 1H) , 6.14-6.11 (m, 1H), 3.78-3.73 (m, 1H) , 3.66-3.63 (m, 1H) , 3.08 (m, 3H) .

Production example 1

2- (4- (2-chlorophenyl) -1, 3-dithiolan-2-ylidene) -2- (pyridin-3- yl ) acetonitrile (lc-3H and lc~3L)

To a stirred solution of potassium hydroxide (0.22 g, 3.97 mmol) in dimethyl sulfoxide (3 ml) was slowly added a solution of 2- (pyridin-3-yl ) acetonitrile (0.19 g, 1.59 mmol) in dimethyl sulfoxide (1 ml) followed by a solution of carbon disulfide (0.303 g, 3.97 mmol) in dimethyl sulfoxide (1 m;l) at 0°C under nitrogen atmosphere. The resulting reaction mixture was then stirred at room temperature for 20 minutes. To this mixture was slowly added a solution of 2-bromo-l- (2- chlorophenyl ) ethyl methanesulfonate (0.50 g, 1.59 mmol) in dimethyl sulfoxide (1 ml) at room temperature. The reaction mixture was then further stirred at room temperature for 3 hrs . The reaction mixture was diluted with ice cooled

distilled water (10 ml) and extracted with ethyl acetate (3 x 10 ml) . The combined organic layer was washed with distilled water, dried over sodium sulfate, filtered and concentrated under reduced pressure to get crude product. The crude product thus obtained was purified by column chromatography on S 111C3 gel with a mixture of ethyl acetate and n-hexane as an eluent to obtain 0.07 g and 0.11 g as two regio-isomers of the title compound lc-3H and lc-3L, respectively, as light yellow solids. The two regio-isomers of the title compound could be separated on TLC and the one at higher Rf value was assigned as lc-3H while the another one at lower Rf values on the TLC was assigned as lc-3L, using the solvent system of n-hexane and ethyl acetate.

lc-3H: ^lH NMR (CDC1₃, 400 MHz) δ: 8.83 (s, 1H) , 8.54 (d, J = 4.0 Hz, 1H), 7.85-7.82 (m, 1H), 7.65-7.62 (m, 1H) , 7.44-7.40 (m, 1H) , 7.35-7.28 (m, 3H) , 5.75-5.72 (m, 1H) , 3.94-3.89 (m, 1H) , 3.74-3.69 (m, 1H) .

lc-3L: ²H NMR (CDC1₃, 400 MHz) δ: 8.84 (s, 1H) , 8.54 (d, J = 4.8 Hz, 1H) , 7.83-7.83 (m, 1H), 7.71-7.68 (m, 1H) , 7.46-7.43 (m, 1H), 7.37-7.30 (m, 3H) , 5.73-5.68 (m, 1H) , 3.96-3.89 (m, 1H) , 3.74-3.69 (m, 1H) . Production example 2 (E&Z) -2- (4- (2-chlorophenyl) -1, 3-dithiolan-2-ylidene ) -2- (6- chloropyridin-3-yl ) acetonitrile (lc-42)

To a stirred solution of potassium hydroxide (0.13 g, 2.38 mmol) in dimethyl sulfoxide (3 ml) was slowly added a solution of 2- ( 6-chloropyridin-3-yl ) acetonitrile (0.15 g, 0.95 mmol) in dimethyl sulfoxide (1 ml) followed by a solution of carbon disulfide (0.18 g, 2.38 mmol) in dimethyl sulfoxide (1 ml) at 0°C under nitrogen atmosphere. The resulting reaction mixture was then stirred at room temperature for 20 minutes. To this mixture was slowly added a solution of 2-bromo-l- ( 2- chlorophenyl ) ethyl methanesulfonate (0.30 g, 0.95 mmol) in dimethyl sulfoxide (1 ml) at room temperature. The reaction mixture was then further stirred at room temperature for 3 hrs . The reaction mixture was diluted with ice cooled

distilled water (10 ml) and extracted with ethyl acetate (3 x 10 ml) . The combined organic layer was washed with distilled water, dried over sodium sulfate, filtered and concentrated under reduced pressure to get crude product. The crude product thus obtained was purified by column chromatography on silica gel with a mixture of ethyl acetate and n-hexane as an eluent to obtain 0.08 g of the title compound as a mixture of two regio-isomers as a brown viscous oil.

H NMR (CDC1_3, 400 MHz) δ: 8.62-8.59 (m, 1H), 7.83-7.79 (m, 1H), 7.64-7.50 (m, 1H) , 7.45-7.29 (m, 4H) , 5.76-5.69 (m, 1H) , 3.99- 3.90 (m, 1H) , 3.79-3.70 (m, 1H) . Representative compounds of the present invention are exemplified in the following Tables 1 to 5, but the present invention is not limited to these compounds.

The compounds shown in Tables 1 to 5, other than the compounds obtained in production examples 1 and 2, were produced by methods similar to the methods described in production example 1 and 2 or methods described in the

descriptio .

The abbreviations in Tables 1 to 5 are as indicated below .

F: fluoro, CI: chloro, Br: bromo, Me: methyl, t-Bu: tert- butyl, CF₃: trifluoromethyl , Ph : phenyl, N0₂ : nitro, C : cyano, OMe : methoxy, CF₃0: trifluoromethoxy, NH₂ : amino.

Table 1: Detail* of the compounds synthesized belonging to the eneral structure (la):

la-5H CI H CI H CI

la-5L CI H CI H CI

la-6 CI CI CI H H

la-7 CI CI H CF₃ H

la-7L CI CI H CF₃ H

la-8 CI CI H OCF₃ H

la-8H CI CI H OCF3 H

la-8L CI CI H OCF3 H

la-9 CI CI H H t-Bu

la-10 CI CI H H CF₃

la-11 CI CI H H OCF₃

la-12 CI CI F H F

la-12L CI CI F H F

la-13 CI CI CI H F

la-13H CI CI CI H F

la-14 CI CI CI H CI

la-14L CI CI CI H CI

la-15H CI CI F H CF₃

la-16 CI CI H OMe OMe

* H and L here refer to two regio-isomers of the compound at higher and lower Rf values on the TLC, respectively, using the solvent system of /i-hexane and ethyl acetate.

Table 2: Detail* of the compounds synthesized belonging to the general structure (lb):

lb-7 H CI H CI H H

lb-8 H H Me Me H H

lb-9 H CI H F H H

lb-10 H F H F H H

* H and L here refer to two regio-isomers of the compound at higher and lower Rf values on the TLC, respectively, using the solvent system of n-hexane and ethyl acetate.

Table 3: Detail* of the compounds synthesized belonging to the general structure (lc):

lc-ΙΟΗ H H Br H H H H lc-lOL H H Br H H H H lc-HH H H CF₃ H H H H lc-HL H H CF₃ H H H H lc-12 H H OMe H H H H lc-12H H H OMe H H H H lc-13 H H CN H H H H lc-13H H H CN H H H H lc-13L H H CN H H H H lc-14H H H N0₂ H H H H lc-15H H H H F H H H lc-15L H H H F H H H lc-16 H H H CI H H H

1C-16H H H H CI H H H lc-16L H H H CI H H H lc-17H H H H Br H H H lc-18L H H H Br H H H lc-19 H H H CF₃ H H H lc-19H H H H CF₃ H H H lc-19L H H H CF₃ H H H lc-20 H H H OMe H H H lc-21H H H H OCF₃ H H H lc-21L H H H OCF₃ H H H lc-22H H H H NH₂ H H H lc-23 H H H CN H H H lc-23H H H H CN H H H lc-23L H H H CN H H H lc-24 H H H N0₂ H H H lc-24H H H H N0₂ H H H lc-25H H H H Ph H H H lc-25L H H H Ph H H H lc-26 H F H F H H H lc-26H H F H F H H H lc-26L H F H F H H H lc-27H H H F F H H H lc-27L H H F F H H H lc-28H H H F H F H H lc-28L H H F H F H H lc-29H H F H H H F H lc-29L H F H H H F H lc-30H H F H Me H H H lc-30L H F H Me H H H lc-31H H H CI F H H H lc-31L H H CI F H H H lc-32H H H CF₃ F H H H lc-32L H H CF₃ F H H H lc-33 H CI H F H H H lc-33L H CI H F H H H lc-34H H CI H CI H H H lc-34L H CI H CI H H H

lc-35 H CI H H CI H H

lc-35H H CI H H CI H H

lc-35L H CI H H CI H H

lc-36 H CI H H H CI H

lc-37 H H CI CI H H H

lc-37H H H CI CI H H H

lc-37L H H CI CI H H H

lc-38H H H Me Me H H H

lc-38L H H Me Me H H H

lc-39H H F H CF₃ H H H

lc-39L H F H CF₃ H H H

lc-40H H CF₃ H CF₃ H H H

lc-40L H CF₃ H CF₃ H H H

lc-41H Me CI H CI H H H

lc-41L Me CI H CI H H H

lc-42 H CI H H H H CI

lc-43 H CI H CI H H CI

lc-44 H H H CF₃ H H CI

lc-44L H H H CF₃ H H CI

Table 4: Detail* of the compounds synthesized belonging to the general structure (Id) :

ld-3H H H CI H H H

ld-3L H H CI H H H

ld-4H H Me H H H H

ld-4L H Me H H H H

ld-5 H CN H H H H

ld-5H H CN H H H H

ld-5L H CN H H H H

ld-6H H N0₂ H H H H

ld-6L H N0₂ H H H H

ld-7 H H N0₂ H H H

ld-7H H H N0₂ H H H

ld-7L H H N0₂ H H H

ld-8 H H H N0₂ H H

ld-8H H H H N0₂ H H

ld-9H H H OMe H H H

ld-9L H H OMe H H H

ld-10 H H H OMe H H

ld-lOL H H H OMe H H

ld-11 H CF₃ H H H H

ld-HH H CF₃ H H H H

ld-llL H CF₃ H H H H

ld-12 H H H CF₃ H H

ld-12H H H H CF₃ H H

ld-12L H H H CF₃ H H

ld-13 H CI H CI H H

ld-13H H CI H CI H H

ld-13L H CI H CI H H

ld-14H H H Me Me H H

ld-14L H H Me Me H H

ld-15 H CI H F H H

ld-15H H CI H F H H

ld-15L H CI H F H H

ld-16 H F H F H H

ld-16H H F H F H H

ld-16L H F H F H H

ld-17 H H CF₃ F H H

ld-17H H H CF₃ F H H

ld-17L H H . CF₃ F H H

ld-18L Me CI H CI H H

Table 5: Detail* of the compounds synthesized belonging to the general structure

The H NMR data of the synthesized compounds represented the Formula (1) are shown in Tables 6 to 10.

Table 6

'No. ^XH-NMR δ ppm (CDCI₃/TMS)

7.59 (bs, 2H) , 7.51-7.47 (m, 3H), 7.30-7.24 (m,

la-1 2H) , 5.62-5.57 (m, IH) , 3.88-3.80 (m, IH) , 3.59- 3.54 (m, IH) , 1.33 (s, 9H) .

7.80-7.62 (m, 5H) , 7.48-7.42 (m, IH), 7.35-7.30

la-2 (m, 2H) , 5.75-5.67 (m, IH) , 3.98-3.88 (m, IH) ,

3.74-3.64 (m, IH) .

7.65 (d, J = 2.8 Hz, IH) , 7.61 (d, J = 10.0 Hz,

2H), 7.43 (d, J = 6.4 Hz, IH), 7.41-7.37 (m, IH), la-2H

7.30 (m, 2H) , 7.26-7,23 (m, IH) , 5.73-5.70 (m,

IH), 3.90-3.77 (m, IH) , 3.70-3.67 (m, IH) . 7.65 (d, J = 2.8 Hz, IH) , 7.61 (d, J = 10.0 Hz, 2H) , 7.43 (d, J = 6.4 Hz, IH), 7.41-7.37 (m, IH) , la-3L

7.30 (m, 2H) , 7.26-7,23 (m, IH) , 5.73-5.70 (m, IH) , 3.90-3.77 (m, IH) , 3.70-3.67 (m, IH) .

7.71-7.68 (m, IH) , 7.45-7.40 (m, IH) , 7.35-7.30 la-4 (m, 5H) , 5.73-5.65 (m, IH), 3.94-3.85 (m, IH) ,

3.74-3.64 (m, IH) .

7.71-7.68 (m, IH) , 7.45-7.42 (m, IH) , 7.35-7.33 la-4L (m, 5H) , 5.73-5.65 (m, IH) , 3.94-3.85 (m, IH) ,

3.74-3.64 (m, IH) .

7.72-7.63 (m, IH) , 7.58-7.50 (m, IH) , 7.48-7.44 (m, IH) , 7.38-7.26 (m, IH) , 7.30-7.26 (m, 3H) , la-5

5.73-5.63 (m, IH) , 3.90-3.85 (m, IH) , 3.80-3.70 (m, IH) .

7.32-7.69 (m, IH) , 7.50 (d, J = 8.0 Hz, IH), 7.50- la-5H 7.40 (m, IH), 7.32-7.26 (m, 4H) , 5.73-5.70 (m,

IH) , 3.90-3.77 (m, IH) , 3.70-3.62 (m, IH) .

7.63-7.61 (m, IH), 7.48-7.44 (m, IH) , 7.40-7.35 (m, IH) , 7.32-7.30 (m, IH) , 7.28-7.26 (m, 3H) , la-5L

5.66-5.59 (m, IH) , 3.90-3.88 (m, IH) , 3.80-3.70 (m, IH) .

7.65 (s, IH), 7.53-7.29 (m, 6H) , 5.66-5.54 (m, la-6

IH) , 3.96-3.83 (m, IH) , 3.68-3.52 (m, IH) .

7.79 (s, IH), 7.75-7.62 (m, IH) , 7.56-7.51 (m, 3H) , 7.48-7.45 (m, IH) , 7.33-7.30 (m, IH) , 5.68- la-7

5.60 (ra, IH) , 3.97-3.88 (m, IH) , 3.69-3.63 (m, IH) .

7.79 (s, IH), 7.62-7.58 (m, 4H) , 7.47-7.45 (m, la-7L IH), 7.32-7.29 (m, IH) , 5.68-5.65 (m, IH), 3.92- 3.88 (m, IH), 3.68-3.63 (m, IH) .

7.61 (s, IH) , 7.47-7.41 (m, 4H) , 7.33-7.29 (m, la-8 IH) , 7.16 (s, IH), 5.67-5.64 (m, IH), 3.91-3.87

(m, IH) , 3.67-3.62 (m, IH) .

7.61 (s, IH) , 7.49-7.42 (m, 4H) , 7.33-7.29 (m, la-8H IH) , 7.16 (s, IH) , 5.62-5.59 (m, IH) , 3.97-3.93

(m, IH) , 3.69-3.64 (m, IH) .

7.60 (s, IH), 7.48-7.45 (m, 4H) , 7.32 (d, J = 2.0 la-8L Hz, IH) , 7.17 (s, IH) , 5.67-5.64 (m, IH) , 3.91- 3.87 (m, IH) , 3.67-3.62 (m, IH) .

7.59 (bs, IH), 7.55-7.48 (m, 5H) , 7.29-7.26 (m, la-9 IH) , 5.66-5.56 (m, IH) , 3.91-3.80 (m, IH) , 3.59- 3.54 (m, IH) , 1.33 (s, 9H) .

7.63 (d, J = 8.4 Hz, IH) , 7.58 (d, J = 7.5 Hz, 2H) , 7.47 (s, IH) , 7.36 (d, J = 4 Hz, IH), 7.33- la-10

7.30 (m, 2H) , 5.62-5.59 (m, IH) , 3.90-3.88 (m, IH) , 3.67-3.63 (m, IH) .

7.64-7.60 (m, 3H) , 7.55-7.47 (m, IH) , 7.38-7.35 la-11 (m, 2H) , 7.28-7.23 (m, IH) , 5.66-5.59 (m, IH),

3.90-3.88 (m, IH) , 3.80-3.70 (m, IH) . 7.63 (bs, IH) , 7.46 (s, IH) , 7.43-7.37 (m, IH), la-12 7.32-7.39 (m, IH) , 6.95-6.87 (m, 2H), 5.66-5.57

(m, IH), 3.95-3.84 (m, IH) , 3.73-3.56 (m, IH) .

7.57 (s, IH), 7.43 (s, IH) , 7.41-7.37 (m, IH) , la-12L 7.29 (s, IH) , 6.94-6.86 (m, 2H) , 5.60-5.57 (m,

IH) , 3.95-3.91 (m, IH), 3.69-3.64 (m, IH).

7.63 (bs, IH) , 7.46 (bs, IH) , 7.40-7.36 (m, IH) , 7.34-7.30 (m, IH) , 7.24-7.20 (m, IH) , 7.06-7.00 la-13

(m, IH) , 5.66-5.55 (m, IH) , 3.96-3.83 (m, IH) , 3.68-3.53 (m, IH) .

7.63 (bs, IH), 7.46 (s, IH) , 7.40-7.36 (m, IH) , 7.34-7.31 (m, IH) , 7.21 (bs, IH) , 7.06-7.02 (m, la-13H

IH) , 5.66-5.63 (m, IH) , 3.87-3.83 (m, IH) , 3.58- 3.53 (m, IH) .

7.64 (bs, IH) , 7.50 (s, IH) , 7.46-4.45 (m, 2H), la-14 7.35-7.30 (m, 2H) , 5.66-5.63 (m, IH) , 3.88-3.80

(m, IH) , 3.59-3.54 (m, IH) .

7.56 (bs, IH) , 7.48 (s, IH) , 7.42 (s, IH), 7.34- la-14L 7.30 (m, 2H) , 7.28 (d, J = 2.0 Hz, IH) , 5.58-5.56

(m, IH) , 3.96-3.92 (m, IH) , 3.69-3.64 (m, IH) .

7.57 (d, J= 6 Hz, 2H) , 7.46 (s, IH) , 7.44 (bs, IH) , 7.41-7.39 (m, IH) , 7.31 (d, J = 6.4 Hz, IH), la-15H

5.66-5.63 (m, IH) , 3.88-3.80 (m, IH) , 3.59-3.54 (m, IH) .

7.63 (bs, IH) , 7.46 (s, IH) , 7.30 (bs, IH) , 7.11- 7.09 (m, IH) , 7.04-6.99 (m, IH), 6.90-6.81 (m, la-16

IH) , 5.62-5.56 (m, IH) , 3.91 (s, 6H), 3.85-3.83 (m, IH) , 3.68-3.53 (m, IH) .

Table 7

No . ¹H-NMR δ ppm ( CDCI₃/TMS )

8.57 (d, J = 4.4 Hz, IH) , 7.75-7.70 (m, 2H), 7.62- 7.60 (d, J = 8.0 Hz, IH) , 7.44-7.41 (m, IH), 7.32- lb-lH

7.28 (m, 2H) , 7.26-7.10 (ra, IH) , 5.63-5.59 (m, IH) , 3.82-3.78 (m, IH) , 3.63-3.58 (m, IH) .

8.63-8.54 (m, IH) , 7.75-7.69 (m, IH) , 7.66-7.59 (m, 2H) , 7.25-7.20 (m, 3H) , 7.14-7.13 (m, IH) , lb-2

5.36-5.30 (m, IH) , 3.73-3.67 (m, IH) , 3.64-3.59 (m, IH) , 2.45-2.43 (m, 3H) .

7.98-7.94 (m, IH) , 7.92 (t, J = 6.0 Hz, IH) , 7.75 (d, J = 8.8 Hz, IH) , 7.61 (d, J = 7.2 Hz, IH), lb-2L 7.28 (bs, IH) , 7.22-7.15 (m, 3H) , 5.23-5.19 (m,

IH) , 3.84-3.80 (m, IH) , 3.55-3.50 (m, IH) , 2.44 (s, 3H) .

8.62-8.56 (m, IH) , 7.75-7.70 (m, IH) , 7.62 (d, J = 8.0 Hz, IH) , 7.51-7.49 (m, IH), 7.40-7.31 (m, 3H) , lb-3

7.15-7.10 (m, IH), 5.10-5.01 (m, IH), 3.72-3.69 (m, 2H) . 8.56-8.54 (m, IH) , 7.73-7.69 (m, IH), 7.60 (d, J = 8.0 Hz, IH), 7.42 (d, J = 8.8 Hz, 2H), 7.12-7.08 lb-4

(m, IH), 6.94-6.91 (m, 2H) , 5.08-5.04 (m, IH) , 3.81 (s, 3H), 3.68-3.63 (m, 2H) .

8.63-8.55 (m, IH) , 8.01-7.96 (m, IH) , 7.76-7.70 (m, 2H) , 7.63-7.59 (m, 2H) , 7.48 (t, J = 7.6 Hz, lb-5

IH) , 7.16-7.12 (m, IH) , 5.54-5.48 (m, IH) , 3.79- 3.71 (m, IH) , 3.64-3.56 (m, IH) .

7.99-7.91 (m, 3H) , 7.76-7.74 (m, IH) , 7.65-7.61 lb-5L (m, 2H) , 7.43 (t, J = 7.6 Hz, IH), 7.22-7.19 (m,

IH) , 5.43-5.30 (m, IH), 3.83-3.70 (m, 2H) .

8.63-8.57 (m, IH) , 7.76-7.71 (m, IH) , 7.67-7.61 lb-6 (m, 5H) , 7.16-7.10 (m, IH) , 5.18-5.10 (m, IH) ,

3.81-3.66 (m, 2H) .

8.57-8.55 (m, IH) , 7.75-7.71 (m, IH) , 7.67-7.61 lb-6H (m, 5H) , 7.14-7.10 (m, IH) , 5.14-5.10 (m, IH) ,

3.74-3.61 (m, 2H) .

8.61 (d, J = 8.8 Hz, IH), 7.75-7.73 (m, IH) , 7.64- 7.60 (m, 2H) , 7.45 (d, J = 2.0 Hz, IH) , 7.29-7.26 lb-7

(m, IH) , 7.14-7.15 (m, IH), 5.55-5.52 (m, IH) , 3.91-3.77 (m, IH) , 3.61-3.53 (m, IH) .

8.64-8.54 (m, IH) , 7.73-7.68 (m, IH) , 7.60-7.58 (m, IH) , 7.22-7.20 (m, IH) , 7.15-7.07 (m, 3H) , lb-8

5.09-5.01 (m, IH) , 3.71-3.60 (m, 2H) , 2.27 (s, 6H) .

7.97-7.93 (m, IH) , 7.90 (t, J = 6.0 Hz, IH), 7.72- 7.70 (m, IH) , 7.60-7.56 (m, IH), 7.21-7.14 (m, lb-9

2H) , 7.01-6.96 (m, IH), 5.80-5.77 (m, IH) , 4.11- 4.08 (m, 2H) .

8.62-8.57 (m, IH) , 7.75-7.71 (m, IH) , 7.62-7.58 (m, 2H) , 7.15-7.10 (m, IH) , 6.93-6.87 (m, 2H) , lb-10

5.40-5.43 (m, IH), 3.83-3.70 (m, IH) , 3.66-3.58 (m, IH) .

Table 8

No. ¹H-NMR δ ppm (CDC1₃/TMS)

8.84-8.80 (m, IH) , 8.56-8.51 (m, IH) , 7.85-7.81 lc-1 (m, IH), 7.50-7.45 (m, IH) , 7.44-7.33 (m, 5H) ,

5.26-5.21 (m, IH) , 3.80-3.72 (m, 2H) .

8.81 (s, IH) , 8.53-8.51 (m, IH) , 7.83-7.80 (m, IH) , 7.46-7.43 (m, 2H) , 7.71-7.38 (m, 3H), 7.35-

Ic-IH

7.29 (m, IH), 5.26-5.23 (m, IH) , 3.79-3.73 (m, 2H) .

8.83 (s, IH) , 8.56-8.54 (m, IH) , 7.85-7.82 (m, IH) , 7.50-7.46 (m, 2H) , 7.42-7.38 (m, 3H) , 7.37-

Ic-IL

7.33 (m, IH) , 5.25-5.21 (m, IH) , 3.83-3.71 (m, 2H) . 8.82 (d, J = 2.0 Hz, IH) , 8.56 (dd, J = 1.6, 4.8 Hz, IH), 7.84-7.81 (m, IH) , 7.56-7.52 (m, IH) , lc-2H 7.38-7.31 (m, 2H) , 7.20 (t, J = 7.6 Hz, IH) , 7.13- 7.08 (m, IH), 5.58-5.54 (m, IH) , 3.86-3.74 (m, 2H) .

8.84 (d, J = 2.4 Hz, IH) , 8.56 (dd, J = 1.6, 4.8 Hz, IH), 7.86-7.83 (m, IH) , 7.63-7.59 (m, IH) , lc-2L 7.40-7.33 (m, 2H) , 7.22 (t, J = 7.6 Hz, IH) , 7.15- 7.11 (m, IH), 5.56-5.53 (m, IH) , 3.90-3.86 (m, IH) , 3.79-3.74 (m, IH) .

8.84 (bs, IH) , 8.56-8.53 (m, IH) , 7.84-7.83 (m, IH), 7.71-7.62 (m, IH) , 7.46-7.42 (m, IH) , 7.37- lc-3

7.30 (m, 3H), 5.75-5.68 (m, IH) , 3.96-3.89 (m, IH) , 3.74-3.69 (m, IH) .

8.83 (s, IH) , 8.54 (d, J = 4.0 Hz, IH) , 7.85-7.82 (m, IH) , 7.65-7.62 (m, IH) , 7.44-7.40 (m, IH) , lc-3H

7.35-7.28 (m, 3H) , 5.75-5.72 (m, IH) , 3.94-3.89 (m, IH) , 3.74-3.69 (m, IH) .

8.84 (s, IH), 8.54 (d, J = 4.8 Hz, IH), 7.83 (bs, IH), 7.71-7.68 (m, IH) , 7.46-7.43 (m, IH), 7.37- lc-3L

7.30 (m, 3H) , 5.73-5.68 (m, IH) , 3.96-3.89 (m, IH) , 3.74-3.69 (m, IH) .

8.83 (s, IH) , 8.54-8.53 (m, IH) , 7.85-7.83 (m, IH), 7.65 (t, J = 8.4 Hz, 2H) , 7.38-7.32 (m, 2H) , lc-4H

7.24-7.22 (m, IH) , 5.73-5.70 (m, IH) , 3.98-3.90 (m, IH) , 3.72-3.68 (m, IH) .

8.84 (s, IH) , 8.56-8.55 (m, IH) , 7.87-7.84 (m, IH), 7.71-7.69 (m, IH) , 7.65-7.60 (m, IH) , 7.38- lc-4L

7.33 (m, 2H), 7.32-7.26 (m, IH) , 5.69-5.66 (m, IH), 3.98-3.93 (m, IH) , 3.73-3.68 (m, IH) .

8.81 (s, IH), 8.52-8.51 (m, IH) , 7.83-7.80 (m, IH) , 7.59-7.57 (m, IH) , 7.33-7.29 (m, IH) , 7.28- lc-5H

7.19 (m, 3H), 5.49-5.45 (m, IH) , 3.85-3.79 (m, IH) , 3.73-3.69 (m, IH) , 2.41(s, 3H) .

8.84 (s, IH) , 8.52-8.51 (m, IH) , 7.86-7.83 (m, IH) , 7.63-7.60 (m, IH) , 7.37-7.33 (m, IH) , 7.28- lc-5L

7.22 (m, 3H) , 5.46-5.42 (m, IH) , 3.85-3.79 (m, IH), 3.75-3.71 (m, IH) , 2.46 (s, 3H) .

8.85-8.80 (m, IH) , 8.57-8.52 (m, IH) , 7.97-7.90 (m, IH), 7.86-7.81 (m, IH) , 7.74-7.70 (m, IH) , lc-6 7.64-7.60 (m, IH) , 7.51-7.46 (m, IH) , 7.38-7.31

(m, IH) , 5.67-5.62 (m, IH) , 3.86-3.80 (m, IH) ,

3.73-3.68 (m, IH) .

8.81 (s, IH), 8.54 (d, J = 4.0 Hz, IH) , 7.92 (d, J = 7.6 Hz, IH) , 7.85-7.82 (m, IH) , 7.72 (d, J = 8.0 Hz, IH), 7.64 (t, J = 7.6 Hz, IH) , 7.50 (t, J = lc-6H

8.0 Hz, IH) , 7.34 (dd, J = 4.4, 7.6 Hz, IH) , 5.67- 5.63 (m, IH) , 3.85-3.80 (m, IH) , 3.73-3.68 (m, IH) . 8.85 (s, IH) , 8.57 (d, J = 4.8 Hz, IH) , 7.97 (d, J = 8.0 Hz, IH) , 7.87-7.84 (m, IH) , 7.74 (d, J = 8.0 Hz, IH) , 7.66 (t, J = 7.6 Hz, IH), 7.52 (t, J = lc-6L

7.6 Hz, IH), 7.38 (dd, J = 4.8, 8.0 Hz, IH) , 5.65- 5.62 (m, IH) , 3.86-3.80 (m, IH) , 3.73-3.68 (m, IH) .

8.68 (s, IH) , 8.54-8.52 (m, IH) , 7.90-7.87 (m, IH) , 7.50-7.45 (m, IH) , 7.36 (d, J = 7.2 Hz, IH) , lc-7H 7.04-7.00 (m, IH) , 6.68 (d, J = 7.6 Hz, IH) , 6.58- 6.55 (m, IH) , 5.61-5.58 (m, IH) , 5.34 (bs, 2H) , 4.03-3.93 (m, 2H) .

8.70 (s, IH), 8.56-8.55 (m, IH) , 7.91-7.89 (m, IH) , 7.53-7.50 (m, IH) , 7.38 (d, J = 7.6 Hz, IH) , lc-7L 7.04-7.02 (m, IH) , 6.71 (d, J = 7.6 Hz, IH), 6.60- 6.57 (m, IH) , 5.61-5.57 (m, IH) , 5.37 (bs, 2H) , 4.03-3.97 (m, 2H) .

8.85-8.81 (m, IH) , 8.57-8.54 (m, IH) , 8.07-8.01 (m, IH), 7.96 (d, J = 8.0 Hz, IH) , 7.89-7.82 (m, lc-8 IH), 7.71 (m, IH), 7.58-7.54 (m, IH) , 7.38-7.32

(m, IH) , 5.88-5.85 (m, IH) , 4.17-4.11 (m, IH) , 3.80-3.75 (m, IH) .

8.81 (s, IH) , 8.55 (d, J = 4.0 Hz, IH) , 8.03 (dd, J = 0.8, 8.0 Hz, IH) , 7.89 (d, J = 8.0 Hz, IH) , lc-8H 7.84-7.81 (m, IH) , 7.71 (t, J = 7.2 Hz, IH) , 7.56- 7.52 (m, IH) , 7.35-7.34 (m, IH) , 5.88-5.85 (m, IH), 4.14-4.12 (m, IH) , 3.79-3.75 (m, IH) .

8.85 (s, IH) , 8.56 (d, J = 1.2 Hz, IH) , 8.07 (d, J = 8.0 Hz, IH) , 7.96 (d, J = 7.6 Hz, IH), 7.88-7.85 lc-8L (m, IH) , 7.73 (t, J = 7.6 Hz, IH) , 7.58-7.54 (m,

IH) , 7.38-7.35 (m, IH) , 5.87-5.85 (m, IH), 4.18- 4.15 (m, IH) , 3.80-3.75 (m, IH) .

8.82-8.80 (m, IH) , 8.56-8.53 (m, IH) , 7.85-7.80 lc-9 (m, IH), 7.49-7.44 (m, IH) , 7.39-7.34 (m, 4H) ,

5.21-5.16 (m, IH) , 3.82-3.76 (m, 2H) .

8.81 (s, IH) , 8.54 (s, IH) , 7.82 (d, J = 8.0 Hz, lc-9H IH) , 7.44 (s, IH) , 7.37-7.32 (m, 4H) , 5.21-5.18

(q, J = 5.6 Hz, IH) , 3.79-3.72 (m, 2H) .

8.83 (s, IH) , 8.56 (d, J = 4.0 Hz, IH) , 7.84 (d, J lc-9L = 8.0 ;Hz, IH) , 7.49 (s, IH) , 7.39-7.32 (m, 4H) ,

5.20-5.17 (q, J = 5.6 Hz, IH) , 3.82-3.73 (m, 2H) .

8.80 (s, IH) , 8.54 (d, J = 4.0 Hz, IH) , 7.83-7.80 (m, IH) , 7.60 (s, IH) , 7.51 (d, J = 8.0 Hz, IH) ,

Ic-IOH

7.39 (d, J =8.0 Hz, IH), 7.37-7.31 (m, 2H) , 5.20- 5.16 (m, IH) , 3.80-3.75 (m, 2H) .

8.82 (s, IH) , 8.56 (d, J = 4.0 Hz, IH) , 7.84 (d, J = 8.0 Hz, IH) , 7 .64 (s, IH) , 7.53 (d, J = 7.6 Hz, lc-lOL IH), 7.44 (d, J = 7.6 Hz, IH) , 7.38-7.34 (m, IH) ,

7.32-7.30 (m, IH) , 5.19-5.15 (m, IH) , 3.82-3.77 (m, 2H) . 8.80 (s, IH) , 8.55 (dd, J = 1.2 Hz, J = 4.8 Hz, IH) , 7.83-7.80 (m, IH) , 7.69 (s, IH) , 7.67-7.63 lc-llH

(m, 2H) , 7.58-7.52 (m, IH) , 7.35-7.32 (m, IH) , 5.30-5.27 (m, IH) , 3.81-3.77 (m, 2H) .

8.83 (bs, IH) , 8.57 (d, J = 4.4 Hz, IH) , 7.85-7.82 (m, IH) , 7.74-7.70 (m, 2H) , 7.66 (d, J = 7.6 Hz, lc-HL

IH) , 7.57-7.51 (m, IH), 7.37-7.31 (m, IH) , 5.29- 5.25 (m, IH), 3.86-3.76 (m, 2H) .

8.94-8.83 (m, IH) , 8.55-8.44 (m, IH) , 7.88-7.83 (m, IH) , 7.38-7.30 (m, 2H) , 7.28-6.90 (m, 3H) , lc-12

5.21-5.18 (m, IH) , 3.83 (s, 3H) , 3.82-3.78 (m, 2H) .

8.80 (s, IH) , 8.52 (d, J = 3.2 Hz, IH) , 7.83 (d, J = 8.4 Hz, IH) , 7.33-7.28 (m, 2H), 7.02 (d, J = 8.0 lc-12H Hz, IH) , 6.97-6.95 (m, IH) , 6.91-6.88 (m, IH) ,

5.23-5.19 (m, IH) , 3.81 (s, 3H) , 3.78-3.71 (m, 2H) .

8.83 (bs, IH) , 8.79 (s, IH) , 7.87-7.80 (m, IH) , 7.76-7.74 (m, IH) , 7.71-7.66 (m, 2H) , 7.57-7.51 lc-13

(m, IH), 7.38-7.32 (m, IH) , 5.26-5.22 (m, IH) , 3.89-3.82 (m, IH) , 3.78-3.72 (m, IH) .

8.82 (s, IH) , 8.55 (d, J = 1.6 Hz, IH) , 7.83-7.80 (m, IH) , 7.74 (s, IH) , 7.69-7.66 (d, 2H) , 7.56- lc-13H 7.51 (d, J = 7.6 Hz, IH) , 7.35-7.32 (m, IH) , 5.26- 5.23 (m, IH) , 3.86-3.82 (m, IH) , 3.77-3.72 (m, IH) .

8.82 (s, IH) , 8.61 (d, J = 4.1 Hz, IH) , 7.86-7.83 (m, IH) , 7.79 (s, IH) , 7.75 (d, J = 8.0 Hz, IH), lc-13L 7.69 (d, J = 8.0 Hz, IH) , 7.61-7.53 (m, IH), 7.38- 7.33 (m, IH) , 5.25-5.22 (m, IH) , 3.89-3.85 (m, IH) , 3.81-3.73 (m, IH) .

8.80 (s, IH) , 8.56 (d, J = 4.0 Hz, IH) , 8.33 (s, IH), 8.25 (dd, J = 1.2, 8.4 Hz, IH) , 7.85-7.79 (m, lc-14H 2H) , 7.63-7.59 (m, IH) , 7.36-7.34 (m, IH) , 5.35- 5.29 (m, IH) , 3.90-3.86 (m, IH) , 3.82-3.77 (m, IH) .

8.80 (d, J = 2.0 Hz, IH), 8.53 (dd, J = 1.2, 4.4 Hz, IH) , 7.82-7.79 (m, IH) , 7.45-7.41 (m, 2H) , lc-15H

7.33-7.30 (m, IH) , 7.10 (m, 2H) , 5.25-5.21 (m, IH) , 3.75-3.70 (m, 2H) .

8.83 (d, J = 2.0 Hz, IH) , 8.56 (dd, J = 1.6, 4.8 Hz, IH) , 7.85-7.82 (m, IH) , 7.51-7.46 (m, 2H) , lc-15L

7.36-7.31 (m, IH), 7.12-7.10 (m, 2H) , 5.23-5.20 (m, IH) , 3.78-3.72 (m, 2H) .

8.82-8.79 (m, IH) , 8.58-8.52 (ra, IH) , 7.83-7.79 lc-16 (m, IH) , 7.44-7.30 (m, 5H) , 5.23-5.18 (m, IH) ,

3.81-3.71 (m, 2H) .

8.79 (s, IH) , 8.54-8.52 (m, IH) , 7.82-7.79 (m, lc-16H IH) , 7.42-7.31 (m, 5H) , 5.23-5.19 (m, IH), 3.79- 3.70 (m, 2H) . 8.83 (s, IH) , 8.56-8.55 (m, IH) , 7.85-7.82 (m, lc-16L IH) , 7.44-7.34 (m, 5H) , 5.22-5.18 (m, IH) , 3.81- 3.71 (m, 2H) .

8.80 (s, IH), 8.54 (bs, IH) , 7.82-7.80 (m, IH) , lc-17H 7.55-7.51 (m, 2H) , 7.33-7.31 (m, 3H) , 5.21-5.18

(m, IH) , 3.79-3.73 (m, 2H) .

8.82 (s, IH) , 8.56-8.55 (m, IH), 7.84-7.81 (m, lc-18L IH) , 7.55-7.51 (m, 2H) , 7.38-7.31 (m, 3H) , 5.20- 5.16 (m, IH) , 3.79-3.73 (m, 2H) .

8.84-8.80 (m, IH) , 7.57-8.53 (m, IH) , 7.87-7.80 (m, IH), 7.70-7.65 (m, 2H) , 7.64-7.57 (m, 2H) , lc-19

7.37-7.31 (m, IH) , 5.29-5.25 (m, IH) , 3.87-3.74 (m, 2H) .

8.80 (s, IH) , 8.55-8.53 (m, IH) , 7.83-7.80 (m, IH) , 7.67 (d, J= 8.0 Hz, 2H), 7.59 (d, J= 8.4 Hz, lc-19H

2H), 7.34-7.31 (m, IH), 5.30-5.26 (m, IH) , 3.85- 3.74 (m, 2H) .

8.83 (s, IH) , 8.57-8.55 (m, IH) , 7.86-7.82 (m, lc-19L IH) , 7.69-7.61 (m, 4H) , 7.37-7.34 (m, IH) , 5.28- 5.25 (m, IH) , 3.87-3.77 (m, 2H) .

8.83 (s, IH) , 8.55 (dd, J = 1.2, 4.8 Hz, IH) , 7.85-7.82 (m, IH) , 7.42 (d, J = 8.4 Hz, 2H) , 7.36- lc-20

7.33 (m, IH) , 6.93 (d, J = 8.4 Hz, 2H) , 5.23-5.19 (m, IH), 3.82 (s, 3H) , 3.78-3.69 (m, 2H) .

8.80 (bs, IH) , 8.54 (d, J = 4.0 Hz, IH) , 7.83-7.80 (m, IH), 7.50-7.48 (m, 2H) , 7.34-7.31 (m, IH) , lc-21H

7.26-7.23 (m, 2H) , 5.27-5.23 (m, IH) , 3.78-3.74 (m, 2H) .

8.83 (bs, IH) , 8.56 (d, J = 4.0 Hz, IH) , 7.85-7.82 (m, IH) , 7.54-7.51 (m, 2H) , 7.37-7.34 (m, IH) , lc-21L

7.27-7.25 (m, 2H) , 5.25-5.21 (m, IH), 3.80-3.75 (m, 2H) .

8.70 (bs, IH) , 8.56-8.52 (m, IH) , 7.91-7.89 (m, 2H), 7.53-7.47 (m, 3H) , 7.34 (d, J = 8.4 Hz, 2H) , lc-22H

6.72 (d, J = 8.8 Hz, IH) , 5.46-5.42 (m, IH), 4.52- 4.51 (m, IH) , 4.01-3.94 (m, IH) .

8.83-8.79 (m, IH) , 8.56-8.54 (m, IH) , 7.85-7.79 (m, IH), 7.73-7.68 (m, 2H) , 7.63-7.56 (m, 2H) , lc-23

7.38-7.33 (m, IH) , 5.29-5.23 (m, IH) , 3.88-3.82 (m, IH) , 3.78-3.72 (m, IH) .

8.79 (bs, IH) , 8.55 (d, J = 4.0 Hz, IH) , 7.82-7.79 (m, IH), 7.70 (d, J = 8.4 Hz, 2H) , 7.58 (d, J = lc-23H

8.4 Hz, 2H) , 7.35-7.31 (m, IH), 5.29-5.24 (m, IH) , 3.86-3.82 (m, IH) , 3.77-3.72 (m, IH) .

8.82 (bs, IH) , 8.56 (d, J = 3.6 Hz, IH) , 7.84-7.81 (m, IH), 7.72 (d, J = 8.4 Hz, 2H), 7.63-7.61 (m, lc-23L

2H) , 7.37-7.35 (m, IH), 5.26-5.23 (m, IH) , 3.89- 3.85 (m, IH) , 3.78-3.75 (m, IH) . 8.83-8.79 (m, IH) , 8.61-8.55 (m, 2H) , 8.29-8.24 lc-24 (m, IH) , 7.82-7.63 (m, 2H) , 7.38-7.33 (m, 2H) ,

5.33-5.28 (m, IH) , 3.89-3.83 (m, 2H) .

8.80 (s, IH), 8.56 (dd, J = 1.2, 4.8 Hz, IH), 8.27 (d, J = 8.8 Hz, 2H) , 7.83-7.80 (m, IH) , 7.65 (d, J lc-24H

= 8.8 Hz, 2H) , 7.36-7.32 (m, IH) , 5.33-5.31 (m, IH) , 3.90-3.85 (m, IH) , 3.80-3.77 (m, IH) .

8.83 (bs,lH), 8.53 (bs,lH), 7.86 (d, J = 8.0 Hz, IH) , 7.62 (d, J = 8.0 Hz, 2H) , 7.58-7.56 (m, 2H) , lc-25H 7.53 (d, J = 8.4 Hz, 2H) , 7.47-7.43 (m, 2H) , 7.39- 7.35 (m, 2H) , 5.32-5.28 (m, IH) , 3.87-3.76 (m, 2H) .

8.85 (bs, IH) , 8.56 (d, J = 4.0 Hz, IH) , 7.87 (d, J = 8.0 Hz, IH) , 7.64 (d, J = 8.4 Hz, 2H) , 7.59- lc-25L

7.55 (m, 4H) , 7.47-7.44 (m, 2H) , 7.39-7.37 (m, 2H) , 5.30-5.26 (m, IH), 3.84-3.37 (m, 2H) .

8.82-8.79 (m, IH) , 8.55-8.52 (m, IH) , 7.84-7.79 (m, IH), 7.61-7.49 (m, IH) , 7.36-7.31 (m, IH) , lc-26

6.95-6.89 (m, 2H) , 5.52-5.50 (m, IH) , 3.86-3.81 (m, IH) , 3.75-3.70 (m, IH) .

8.81 (s, IH), 8.55 (d, J = 4.0 Hz, IH), 7.83-7.80 (m, IH) , 7.56-7.50 (m, IH) , 7.35-7.32 (m, IH) , lc-26H

6.94-6.89 (m, 2H) , 5.53-5.49 (ra, IH) , 3.86-3.81 (m, IH) , 3.76-3.70 (m, IH) .

8.82 (s, IH) , 8.56 (d, J = 4.0 Hz, IH) , 7.83-7.83 (m, IH), 7.62-7.56 (m, IH) , 7.37-7.34 (m, IH) , lc-26L

6.96-6.87 (m, 2H) , 5.50-5.47 (m, IH) , 3.89-3.85 (m, IH) , 3.75-3.72 (m, IH) .

8.79 (s, IH) , 8.54-8.53 (m, IH) , 7.82-7.79 (m, lc-27H IH) , 7.34-7.29 (m, 2H) , 7.20-7.17 (m, 2H), 5.21- 5.17 (m, IH) , 3.80-3.68 (m, 2H) .

8.82 (s, IH) , 8.56-8.55 (m, IH) , 7.84-7.81 (m, IH), 7.37-7.34 (m, 2H), 7.23-7.20 (m, 2H) , 5.19- lc-27L

5.16 (m, IH) , 3.82-3.77 (m, IH) , 3.74-3.69 (m, IH) .

8.81 (bs, IH) , 8.56 (bs, IH) , 7.86 (d, J = 7.2 Hz, IH) , 7.37 (bs, IH) , 7.00 (d, J = 5.6 Hz, 2H), lc-28H

6.84-6.80 (m, IH) , 5.19-5.18 (m, IH) , 3.83-3.79 (m, IH) , 3.75-3.70 (m, IH) .

8.83 (bs, IH) , 8.56 (bs, IH) , 7.87 (d, J = 8.0 Hz, IH) , 7.38 (bs, IH) , 7.04 (d, J = 5.6 Hz, 2H) , lc-28L

6.86-6.81 (m, IH) , 5.19-5.15 (m, IH) , 3.86-3.82 (m, IH) , 3.78-3.71 (m, IH) .

8.83 (bs, IH) , 8.56-8.55 (m, IH) , 7.85 (d, J = 8.0 Hz, IH), 7.41-7.33 (m, 2H) , 7.00-6.96 (m, 2H) , lc-29H

5.62-5.57 (m, IH) , 4.22-4.16 (m, IH) , 3.63-3.59 (m, IH) . 8.79 (bs, IH) , 8.52 (d, J = 3.6 Hz, IH) , 7.84-7.79 (m, IH) , 7.39-7.29 (m, 2H) , 6.98-6.93 (m, 2H) , lc-29L

5.62-5.58 (m, IH) , 4.14-4.09 (m, IH), 3.63-3.59 (m, IH) .

8.83 (bs, IH) , 8.54 (bs, IH) , 7.89 (d, J = 7.6 Hz, IH) , 7.42-7.38 (bs, 2H), 6.99 (d, J = 8.0 Hz, IH) , lc-30H

6.93-6.91 (m, IH) , 5.55-5.51 (m, IH) , 3.79-3.78 (m, 2H) , 2.35 (s, 3H) .

8.83 (bs,lH), 8.54 (bs,lH), 7.85 (d, J = 8.4 Hz, IH) , 7.52-7.44 (m, IH) , 7.36-7.33 (m, IH) , 7.01 lc-30L (d, J = 7.6 Hz, IH) , 6.95-6.92 (m, IH), 5.52-4.48

(m, IH) , 3.84-3.81 (m, IH) , 3.77-3, 72 (m, IH) , 2.36 (s, 3H) .

8.82 (s, IH) , 8.56-8.55 (m, IH) , 7.84-7.82 (m, IH) , 7.56-7.54 (m, IH), 7.39-7.34 (m, 2H) , 7.20 lc-31H

(t, J = 8.4 Hz, IH), 5.19-5.15 (m, IH), 3.82-3.70 (m, 2H) .

8.79 (s, IH) , 8.55-8.54 (m, IH) , 7.82-7.79 (m, IH) , 7.52-7.50 (m, IH), 7.35-7.31 (m, 2H) , 7.18 lc-31L

(t, J = 8.4 Hz, IH) , 5.20-5.16 (m, IH) , 3.79-3.69 (m, 2H) .

8.80 (s, IH) , 8.56 (s, IH) , 7.82 (d, J = 8.4 Hz, lc-32H IH) , 7.69-7.65 (m, 2H), 7.34 (bs, IH), 7.22-7.18

(m, IH), 5.27-5.24 (m, IH) , 3.82-3.71 (m, 2H) .

8.57 (s, IH) , 7.84 (d, J = 8.0 Hz, IH), 7.74-7.70 (m, 2H) , 7.38-7.35 (m, IH) , 7.29-7.27 (m, IH) , lc-32L

5.26-5.23 (m, IH), 3.84-3.81 (m, IH) , 3.75-3.72 (m, IH) .

8.62-8.32 (m, IH) , 8.38-8.34 (m, IH) , 7.53 (d, J = 2 Hz, IH) , 7.15-7.08 (m, IH) , 7.00 (d, J = 2.8 Hz, lc-33

IH) , 6.90 (m, IH) , 6.81-6.77 (m, IH) , 5.30 (s, IH) , 2.27-2.24 (m, 2H) .

8.73 (s, IH), 8.62-8.60 (m, IH) , 7.84-7.81 (m, IH), 7.37-7.34 (m, IH), 7.28-7.24 (m, 2H), 7.18- ic-33L

7.07 (m, IH) , 2.91-2.87 (m, IH), 2.27-2.25 (m, IH) , 2.13-2.11 (m, IH) .

8.81 (s, IH), 8.55-8.53 (m, IH) , 7.84-7.81 (m, IH) , 7.57-7.55 (m, IH) , 7.45-7.44 (m, IH) , 7.35- lc-34H

7.29 (m, 2H) , 5.68-5.63 (m, IH) , 3.94-3.89 (m, IH) , 3.70-3.66 (m, IH) .

8.83-8.81 (m, IH) , 8.56-8.54 (m, IH), 7.88-7.81 (m, IH), 7.64-7.55 (m, IH) , 7.47-7.44 (m, IH) , lc-34L

7.37-7.29 (m, 2H) , 5.68-5.61 (m, IH), 3.96-3.91 (m, IH) , 3.70-3.64 (m, IH) .

8.83-8.82 (ra, IH) , 8.57-8.55 (m, IH) , 7.83-7.82 (m, IH) , 7.67-7.60 (m, IH) , 7.40-7.27 (m, 3H) , lc-35

5.66-5.60 (m, IH) , 3.97-3.89 (m, IH) , 3.72-3.65 (m, IH) . 8.82 (s, IH) , 8.58-8.54 (m, IH) , 7.84-7.81 (m, lc-35H IH), 7.61 (s, IH) , 7.38-7.27 (m, 3H) , 5.66-5.63

(m, IH) , 3.93-3.89 (m, IH) , 3.71-3.66 (m, IH) .

8.84 (s, IH) , 8.57-8.56 (m, IH) , 7.86-7.83 (m, lc-35L IH) , 7.67 (s, IH) , 7.40-7.29 (m, 3H) , 5.64-5.61

(m, IH), 3.97-3.93 (m, IH), 3.72-3.67 (m, IH) .

8.84-8.82 (m, IH), 8.55-8.51 (m, IH) , 7.85-7.83 (m, IH), 7.41-7.32 (m, 2H) , 7.31-7.29 (m, 2H), lc-36

6.24-6.19 (m, IH), 4.60-4.52 (m, IH) , 3.54-3.49 (m, IH) .

8.82-8.79 (m, IH) , 8.55-8.53 (m, IH) , 7.84-7.79 (m, IH), 7.59-7.54 (m, IH) , 7.48 (d, J= 8.4 Hz, lc-37

IH), 7.37-7.27 (m, 2H), 5.19-5.16 (m, IH) , 3.83- 3.69 (m, 2H) .

8.79 (s, IH) , 8.54-8.53 (m, IH) , 7.81 (d, J = 7.6 Hz, IH), 7.55 (s, IH) , 7.47 (d, J = 8.4 Hz, IH) , lc-37H

7.34-7.28 (m, 2H) , 5.19-5.16 (m, IH) , 3.80-3.69 (m, 2H) .

8.82 (s, IH) , 8.56-8.55 (m, IH) , 7.84 (d, J = 8.0 Hz, IH) , 7.59 (s, IH) , 7.50 (d, J = 8.0 Hz, IH) , lc-37L

7.37-7.33 (m, 2H) , 5.18-5.15 (m, IH) , 3.83-3.70 (m, 2H) .

8.81 (s, IH) , 8.52 (d, J = 3.6 Hz, IH) , 7.83 (d, J = 7.6 Hz, IH) , 7.32-7.29 (m, IH) , 7.20-7.12 (m, lc-38H

3H), 5.21-5.17 (m, IH) , 3.81-3.75 (m, IH) , 3.71- 3.67 (m, IH) , 2.26 (s, 6H) .

8.83 (s, IH), 8.55 (s, IH) , 7.85-7.82 (m, IH) , 7.36-7.32 (m, IH) , 7.22-7.14 (m, 3H) , 5.20-5.16 lc-38L

(m, IH), 3.81-3.73 (m, IH) , 3.72-3.69 (m, IH) , 2.28 (s, 6H) .

8.81 (s, IH) , 8.56 (s, IH) , 7.84-7.81 (m, IH) , 7.69 (t, J = 8 Hz, IH) , 7.47 (s, IH) , 7.39 (d, J = lc-39H

10.0 Hz, IH) , 7.36-7.34 (m, IH) , 5.58-5.55 (m, IH) , 3.94-3.90 (m, IH) , 3.78-3.73 (m, IH) .

8.83 (s, IH) , 8.57 (d, J = 3.2 Hz, IH) , 7.86-7.83 (m, IH), 7.79 (t, J = 7.6 Hz, IH) , 7.50 (s, IH), lc-39L 7.42 (d, J = 10.0 Hz, IH) , 7.38-7.35 (m, IH) ,

5.56-5.53 (m, IH) , 3.98-3.94 (m, IH) , 3.77-3.73 (m, IH) . ;

8.82 (bs, IH), 8.60-8.55 (m, IH) , 7.96 (s, IH) , lc-40H 7.85-7.80 (m, 3H) , 7.45-7.33 (m, IH) , 5.35-5.32

(m, IH) , 3.89-3.85 (m, IH) , 3.83-3.78 (m, IH) .

8.82 (bs,lH), 8.60-8.55 (m, IH) , 7.96 (s, 2H) , 7.90-7.89 (m, IH) , 7.85-7.82 (m, IH) , 7.39-7.35 lc-40L

(m, IH) , 5.34-5.31 (m, IH) , 3.90-3.87 (m, IH) , 3.82-3.79 (m, IH)

8.81 (s, IH) , 8.54 (s, IH) , 7.84-7.82 (m, IH) , 7.53 (d, J = 8.8 Hz, IH) , 7.46 (d, J = 2.0 Hz, lc-41H

IH) , 7.35-7.32 (m, 2H), 5.36 (d, J = 6.8 Hz, IH) , 4.18-4.11 (m, IH) , 1.57 (bs, 3H) . 8.82 (s, IH), 8.55 (s, IH) , 7.84-7.81 (m, IH) , 7.60 (d, J = 8.8 Hz, IH) , 7.48 (d, J = 2.4 Hz, lc-41L

IH) , 7.37-7.32 (m, 2H) , 5.32(d, J = 6.4 Hz, IH), 4.19-4.12 (m, IH) , 1.57 (bs, 3H) .

8.62-8.59 (m, IH) , 7.83-7.79 (m, IH) , 7.64-7.50 lc-42 (m, IH) , 7.45-7.29 (m, 4H) , 5.76-5.69 (m, IH) ,

3.99-3.90 (m, IH) , 3.79-3.70 (m, IH) .

8.61-8.58 (m, IH) , 7.82-7.77 (m, IH) , 7.56-7.53 (m, IH) , 7.48-7.46 (m, IH) , 7.39-7.29 (m, 2H) , lc-43

5.69-5.62 (m, IH) , 3.98-3.90 (m, IH) , 3.72-3.69 (m, IH) .

8.67-8.64 (m, 2H) , 7.68 (d, J = 8.0 Hz, 2H) , 7.63 (m, 2H) , 7.50-7.47 (m, 2H) , 5.28-5.24 (t, J = 5.2, lc-44

Hz, IH) , 3.90 (d, J = 5.2 Hz, IH) , 3.83 (d, J = 2.8 Hz, IH) .

8.61-8.60 (m, IH) , 8.37-8.36 (m, IH) , 7.82-7.79 (m, IH) , 7.70-7.65 (m, 2H) , 7.63-7.58 (m, IH) , lc-44L

7.40-7.38 (m, IH) , 5.32-5.25 (m, IH), 3.86-3.80 (m, 2H) .

Table 9

No. ^XH-NMR δ ppm (CDC1₃/TMS)

8.66 (m, 2H), 7.75-7.61 (m, IH) , 7.53-7.47 (m, 2H), 7.39-7.35 (m, IH) , 7.26-7.16 (m, IH) , 7.13- ld-1

7.10 (m, IH), 5.55-5.52 (m, IH) , 3.85-3.80 (m, 2H) .

8.66-8.62 (m, 2H) , 7.57-7.55 (m, IH) , 7.50-7.47 (m, 2H) , 7.40-7.34 (m, IH) , 7.26-7.16 (m, IH) ,

Id-IH

7.13-7.10 (m, IH) , 5.55-5.52 (m, IH), 3.85-3.77 (m, 2H) .

8.65 (d, J = 2.8 Hz, 2H) , 7.75-7.61 (m, IH) , 7.53- 7.47 (m, 2H) , 7.39-7.35 (m, IH) , 7.26-7.16 (m, ld-lL

IH) , 7.13-7.10 (m, IH) , 5.55-5.52 (m, IH) , 3.96- 3.92 (m, IH) , 3.85-3.80 (m, IH) .

8.65-8.62 (m, 2H) , 7.69-7.62 (m, IH) , 7.51-7.43 ld-2 (m, 3H) , 7.35-7.31 (m, 2H) , 5.80-5.67 (m, IH) ,

4.14-3.88 (m, IH) , 3.80-3.69 (m, IH) .

8.64-8.62 (m, 2H) , 7.65-7.63 (m, IH) , 7.49-7.43 ld-2H (m, 3H), 7.35-7.31 (m, 2H) , 5.80-5.77 (m, IH) , 3- 92-3.85 (m, IH) , 3.74-3.69 (m, IH) .

8.66-8.64 (m, 2H) , 7.69-7.67 (m, IH) , 7.51-7.49 (m, 2H) , 7.47-7.45 (m, IH) , 7.38-7.31 (m, 2H) , ld-2L

5.71-5.68 (m, IH) , 4.04-3.99 (m, IH) , 3.80-3.75- (m, IH) .

8.68-8.63 (m, 2H) , 7.48-7.45 (m, 3H) , 7.40-7.39 ld-3

(m, 3H) , 5.30-5.16 (m, IH) , 3.86-3.74 (m, 2H) . 8.63 (d, J = 3.2 Hz, 2H) , 7.47-7.45 (m, 3H), 7.39- ld-3H 7.36 (m, 3H) , 5.26-5.22 (m, IH) , 3.78-3.71 (m,

2H) .

8.64 (d, J = 6.4 Hz, 2H) , 7.50-7.48 (m, 3H) , 7.40 ld-3L (d, J = 2.0 Hz, 3H), 5.20-5.16 (m, IH), 3.89-3.84

(m, 2H) .

8.62-8.60 (m, 2H) , 7.61-7.51 (m, IH) , 7.47-7.46 (m, 2H) , 7.32-7.24 (m, 3H) , 5.53-5.50 (m, IH) , ld-4H

3.84-3.78 (m, IH) , 3.72-3.68 (m, IH) , 2.43 (s, 3H) .

8.66-8.64 (m, 2H) , 7.62-7.60 (m, IH) , 7.51-7.49 ld-4L (m, 2H) , 7.28-7.27 (m, 3H) , 5.45-5.41 (m, IH) ,

3.89-3.78 (m, 2H) , 2.46 (s, 3H) .

8.67-8.63 (m, 2H) , 7.73-7.70 (m, 2H) , 7.63-7.58 ld-5 (m, 2H), 7.49-7.46 (m, 2H) , 5.33-5.24 (m, IH) ,

3.85-3.81 (m, IH) , 3.78-3.71 (m, IH) .

8.65-8.63 (ra, 2H) , 7.72-7.70 (m, 2H) , 7.60 (d, J = ld-5H 8.4 Hz, 2H) , 7.46 (d, J = 6.0 Hz, 2H) , 5.33-5.29

(m, IH) , 3.85-3.81 (m, IH) , 3.78-3.71 (m, IH) .

8.67-8.63 (m, 2H) , 7.73-7.70 (m, 2H) , 7.63-7.58 ld-5L (m, 2H) , 7.49-7.46 (m, 2H) , 5.26-5.24 (m, IH) ,

3.85-3.81 (ra, IH) , 3.78-3.74 (ra, IH) .

8.90-8.66 (m, 2H) , 8.08 (d, J= 6.8 Hz, IH) , 7.92 (d, J = 1.2 Hz, IH) , 7.74-7.69 (m, IH), 7.59-7.55 ld-6H

(m IH) , 7.52-7.46 (m, 2H) , 5.87-5.85 (m, IH) , 4.26-4.21 (m, IH) , 3.79-3.75 (m, IH) .

8.90-8.66 (m, 2H) , 8.08 (d, J= 6.8 Hz, IH) , 7.92 (d, J = 1.2 Hz, IH) , 7.74-7.69 (m, IH), 7.59-7.55 ld-6L

(m IH) , 7.52-7.46 (m, 2H), 5.87-5.85 (m, IH), 4.26-4.21 (m, IH) , 3.86-3.81 (m, IH) .

8.72-8.64 (m, 2H) , 8.37 (d, J = 8 Hz, IH) , 8.26 (d, J = 8 Hz, IH) , 7.87-7.81 (m, IH) , 7.65-7.60 ld-7

(m, IH) , 7.51-7.45 (ra, 2H) , 5.37-5.30 (m, IH) , 3.94-3.87 (m, 2H) .

8.66 (d, J = 4 Hz, 2H) , 8.37 (s, IH), 8.27 (d, 6.8 Hz, IH) , 7.86 (d, J = 8 Hz, IH) , 7.63 (t, J = 8 ld-7H

Hz, IH) , 7.50 (d, J = 3.2 Hz, 2H) , 5.33-5.30 (m, IH) , 3.89-3.80 (m, 2H) .

8.66 (d, J = 4.0 Hz, 2H) , 8.37 (s, IH) , 8.27 (d, 6.8 Hz, IH), 7.86 (d, J = 8 Hz, IH) , 7.63 (t, J = ld-7L

8 Hz, IH) , 7.50 (d, J = 3.2 Hz, 2H) , 5.33-5.30 (m, IH) , 3.99-3.95 (m, IH) , 3.89-3.84 (m, IH) .

8.81-8.80, (m IH) , 8.63 (bs, IH) , 8.37-8.33 (m, IH) , 8.27-8.24 (m, IH) , 7.87-7.79 (m, 2H), 7.63- ld-8

7.59 (m, IH), 7.45-7.33 (m, IH) , 5.73-5.65 (m, IH) , 3.94-3.85 (m, IH) , 3.74-3.64 (m, IH) .

8.66-8.64 (ra, 2H) , 8.29-8.26 (m, 2H) , 7.70-7.65 ld-8H (m, 2H) , 7.50-7.45 (m, 2H) , 5.31-5.28 (m, IH) ,

3.99-3.94 (m, IH) , 3.86-3.77 (m, IH) . 8.62 (s, 2H) , 7.48 (d, J = 5.2 Hz, 2H) , 7.34-7.26 ld-9H (m, 2H) , 6.95-6.91 (m, 2H) , 5.29-5.23 (m, IH) ,

3.82 (s, 3H) , 3.75-3.72 (m, 2H) .

8.65 (s, 2H) , 7.48 (d, J = 6.0 Hz, 2H), 7.39-7.32 (m, IH) , 7.06 (d, J = 8.0 Hz, IH) , 7.02 (s, IH), ld-9L

6.95-6.92 (m, IH) , 5.21-5.17 (m, IH) , 3.82 (s, 3H) , 3.75-3.72 (m, 2H) .

8.62-8.55 (m, IH) , 7.73-7.69 (m, IH) , 7.61 (d, J = 8.0 Hz, IH) , 7.43 (d, J = 8.8 Hz, 2H) , 7.14-7.08 ld-10

(m, IH) , 6.92-6.88 (m, 2H) , 5.11-5.04 (m, IH) , 3.82 (s, 3H) , 3.68-3.61 (m, 2H) .

8.61 (d, J = 6.0 Hz, 2H) , 7.47-7.46 (m, 2H) , 7.40 (d, J = 8.8 Hz, 2H) , 6.92 (d, J = 8.8 Hz, 2H) , ld-lOL

5.30-5.25 (m, IH) , 3.82 (s, 3H) , 3.75-3.67 (m, 2H) .

8.64 (d, J = 13.2 Hz, 2H) , 7.96-7.91 (m, IH) , 7.75-7.72 (m, IH) , 7.64, (d, J = 7.6 Hz, IH) , ld-11

7.52-7.41 (m, 3H) , 5.72-5.63 (m, IH) , 3.93-3.70 (m, 2H) .

8.63 (s, 2H) , 7.93 (d, J = 7.6 Hz, IH) , 7.74 (d, J = 8.0 Hz, IH) , 7.64, (t, J = 8.0 Hz, IH), 7.52- ld-HH

7.41 (m, 3H) , 5.65-5.61 (m, IH) , 3.84-3.80 (m, IH) , 3.78-3.67 (m, IH) .

8.65 (d, J = 4.0 Hz, 2H) , 7.95 (d, J = 7.6 Hz, IH) , 7.74 (d, J = 8.0 Hz, IH) , 7.64, (t, J = 8 Hz, ld-HL

IH) , 7.52-7.41 (m, 3H) , 5.65-5.61 (m, IH), 3.93- 3.89 (m, IH) , 3.78-3.73 (m, IH) .

8.66-8.62 (m, 2H) , 7.69-7.67 (m, 2H) , 7.64-7.59 ld-12 (m, 2H) , 7.50-7.45 (m, 2H) , 5.34-5.24 (m, IH),

3.93-3.80 (m, 2H) .

8.64-8.62 (m, 2H) , 7.69-7.67 (m, 2H) , 7.65-7.61 ld-12H (m, 2H) , 7.49-7.45 (m, 2H) , 5.34-5.31 (m, IH) ,

3.84-3.74 (m, 2H) .

8.67-8.64 (m, 2H) , 7.71-7.67 (m, 2H) , 7.65-7.61 ld-12L (m, 2H), 7.51-7.47 (m, 2H) , 5.28-5.24 (m, IH) ,

3.94-3.89 (m, IH) , 3.83-3.80 (m, IH) .

8.66-8.63 (m, 2H) , 7.62-7.56 (m, IH) , 7.52-7.45 ld-13 (m, 3H) , 7.33-7.30 (m, IH) , 5.73-5.61 (m, IH) ,

4.04-3.88 (m, IH) , 3.78-3.67 (m, IH) .

8.65-8.63 (m, 2H) , 7.58-7.56 (m, IH) , 7.47-7.46 ld-13H (m, 3H) , 7.32-7.30 (m, IH) , 5.73-5.70 (m, IH) ,

3.92-3.88 (m, IH) , 3.70-3.65 (m, IH) .

8.66-8.65 (m, 2H) , 7.62-7.58 (m, IH) , 7.50-7.46 ld-13L (m, 3H) , 7.33-7.30 (m, IH) , 5.63-5.60 (ra, IH) ,

4.04-3.99 (m, IH) , 3.76-3.71 (m, IH) .

8.61-8.59 (m, 2H) , 7.47-7.46 (m, 2H), 7.22-7.19 (m, IH) , 7.18-7.16 (m, 2H) , 5.26-5.22 (m, IH) , ld-14H

3.80-3.74 (m, IH) , 3.71-3.66 (m, IH) , 2.28 (s, 6H) . 8.65 (d, J = 6.0 Hz, 2H), 7.50-7.48 (m, 2H) , 7.24- ld-14L 7.12 (m, 3H) , 5.19-5.15 (m, IH) , 3.86-3.75 (m,

2H) , 2.27 (s, 6H) .

8.66-8.63 (m, 2H) , 7.68-7.61 (m, IH) , 7.50-7.46 (m, 2H) , 7.23-7.19 (m, IH), 7.08-7.03 (m, IH), ld-15

5.74-5.62 (m, IH) , 4.00-3.87 (m, IH) , 3.76-3.65 (m, IH) .

8.64-8.63 (m, 2H) , 7.64 (dd, J = 5.6 Hz, J = 8.8 Hz, IH), 7.48-7.46 (m, 2H), 7.22-7.19 (m, IH), ld-15H

7.08-7.04 (m, IH) , 5.75-5.72 (m, IH), 3.91-3.87 (m, IH) , 3.70-3.65 (m, IH) .

8.66-8.65 (m, 2H) , 7.64 (dd, J = 6.0 Hz, J = 8.8 Hz, IH) , 7.50-7.49 (m, 2H) , 7.23-7.20 (m, IH) , ld-15L

7.08-7.06 (m, IH) , 5.65-5.62 (m, IH) , 4.03-3.98 (m, IH) , 3.76-3.72 (m, IH) .

8.66-8.62 (m, 2H) , 7.61-7.55 (m, IH) , 7.50-7.48 ld-16 (m, 2H) , 6.96-6.86 (m, 2H) , 5.57-5.47 (m, IH) ,

3.95-3.91 (m, IH) , 3.76-3.71 (m, IH) .

8.64 (d, J = 3.2 Hz, 2H) , 7.56-7.51 (m, IH) , 7.47- ld-16H 7.46 (m, 2H) , 6.96-6.88 (m, 2H) , 5.57-5.54 (m,

IH) , 3.84-3.80 (m, IH) , 3.76-3.71 (m, IH) .

8.66 (d, J = 3.2 Hz, 2H) , 7.61-7.55 (m, IH), 7.50- ld-16L 7.48 (m, 2H) , 6.96-6.88 (m, 2H) , 5.57-5.54 (m,

IH) , 3.84-3.80 (m, IH) , 3.76-3.71 (m, IH) .

8.64 (s, 2H) , 7.74-7.68 (m, 2H) , 7.49-7.45 (m, ld-17 2H) , 7.29 (d, J = 2.8 Hz, IH) , 5.31-5.22 (m, IH) ,

3.83-3.78 (m, 2H) .

8.67 (s, 2H) , 7.74-7.70 (m, 2H), 7.45 (d, J = 3.2 ld-17H Hz, 2H), 7.29 (s, IH) , 5.30-5.22 (m, IH), 3.92- 3.87 (m, IH), 3.83-3.80 (m, IH) .

8.64 (d, J = 2.8 Hz, 2H) , 7.72-7.66 (m, 2H), 7.45 ld-17L (d, J = 3.2 Hz, 2H) , 7.29 (s, IH), 5.32-5.22 (m,

IH) , 3.82-3.78 (m, 2H) .

8.65 (d, J = 6.0 Hz, 2H) , 7.57 (d, J = 8.4 Hz, IH) , 7.48 (d, J = 5.6 Hz, 3H), 7.33 (d, J = 6.4 ld-18L

Hz, IH) , 5.31 (d, J = 6.4 Hz, IH) , 4.23 (t, J = 6.8 Hz, IH), 1.58 (d, J = 6.8 Hz, 3H) .

Table 10

No. ¹H-NMR δ ppm (CDC1₃/TMS)

8.82-8.81 (bs, IH) , 8.62-8.61 (m, IH) , 8.54-8.52 (m, IH) , 7.85-7.82 (m, IH) , 7.76-7.72 (m, IH) , le-1

7.56-7.43 (m, IH) , 7.34-7.28 (ra, 2H) , 5.35-5.32 (m, IH) , 4.20-4.06 (m, IH), 3.93-3.84 (m, IH) . 8.82 (bs, IH), 8.61 (d, J = 4.0 Hz, IH), 8.53-8.52 (m, IH) , 7.84-7.81 (m, IH) , 7.77-7.70 (m, IH) ,

Ie-1H 7.43 (d, J = 7.6 Hz, IH), 7.34-7.29 (m, 2H), 5.39- 5.29 (m, IH), 4.10-4.06 (m, IH) , 3.89-3.85 (m, IH) .

8.73-8.62 (m, 2H), 8.59-8.49 (m, IH) , 7.83-7.75 le-2 (m, 2H) , 7.51-7.35 (m, 3H) , 5.86-5.64 (m, IH) ,

5.00-4.96 (m, IH) , 4.93-4.84 (m, IH) .

8.80 (bs, IH), 8.68 (s, IH) , 8.63 (d, J = 4.4 Hz, IH), 8.55 (d, J = 4.8 Hz, IH), 7.83 (d, J = 7.6 le-2H

Hz, 2H) , 7.37-7.32 (m, 2H) , 5.28-5.24 (m, IH) , 3.87-3.82 (m, IH) , 3.79-3.74 (m, IH) .

8.83-8.80 (m, IH) , 8.68-8.65 (m, 2H) , 8.57-8.55 (m, IH) , 7.83-7.81 (m, IH) , 7.42-7.41 (m, IH) , le-3

7.38-7.36 (m, 2H) , 5.19-5.16 (m, IH) , 3.87-3.84 (m, IH) , 3.79-3.74 (m, IH) .

8.73-8.70 (m, IH) , 8.62-8.55 (m, 3H ) , 7.93-7.88 (m, IH) , 7.59-7.58 (m, IH) , 7.54-7.48 (m, 2H) , le-3L

5.62-5.59 (m, IH) , 4.13-4.11 (m, IH) , 4.08-4.04 (m, IH) .

8.81 (s, IH) , 8.56 (bs, IH) , 7.82-7.79 (m, 2H) , le-4 7.39-7.34 (m, 2H) , 5.56-5.53 (ra, IH) , 4.13-4.09

(m, IH) , 4.05-4.00 (m, IH) .

8.81-8.80 (m, IH) , 8.57-8.56 (m, IH) , 7.82-7.79 le-5 (m, 2H), 7.39-7.36 (m, 2H) , 5.53-5.49 (m, IH) ,

4.18-4.10 (m, IH) , 4.05-3.97 (m, IH) .

8.83-8.79 (m, 2H) , 8.54-8.52 (m, IH) , 7.84-7.79 (m, IH) , 7.50-7.39 (m, IH) , 7.35-7.30 (m, IH) , le-5H

5.48-5.41 (m, IH) , 4.08-4.04 (m, IH) , 3.96-3.90 (m, IH) .

8.83-8.79 (m, 2H) , 8.54-8.52 (m, IH) , 7.84-7.79 (m, IH) , 7.50-7.39 (m, IH) , 7.35-7.30 (m, IH) , le-5L

5.48-5.41 (m, IH) , 4.08-4.04 (m, IH) , 3.96-3.90 (m, IH) .

8.82-8.80 (m, IH) , 8.76 (s, IH) , 8.55-8.54 (m, IH) , 7.95-7.90 (s, IH) , 7.84-7.77 (m, IH) , 7.38- le-6

7.34 (m, IH) , 5.61-5.57 (m, IH) , 3.96-3.92 (m, IH) , 3.77-3.74 (m, IH) .

8.80 (s, IH) , 8.76 (bs, IH) , 8.55 (d, J = 3.6 Hz, IH) , 7.90 (s, IH), 7.80-7.77 (m, IH) , 7.35-7.32 le-6H

(m, IH) , 5.61-5.57 (m, IH) , 3.96-3.92 (m, IH) , 3.77-3.72 (m, IH) .

8.84-8.80 (m, IH) , 8.72 (s, IH) , 8.60-8.54 (ra, 3H) , 7.84-7.80 (m, IH) , 7.36-7.32 (m, IH) , 5.39- le-7

5.33 (m, IH) , 4.13-4.10 (m, IH) , 3.94-3.90 (m, IH) .

8.82-8.80 (m, IH) , 8.72 (s, IH) , 8.61-8.59 (m, 2H) , 8.56-8.55 (m, IH) , 7.85-7.80 (m, IH) , 7.36- le-7L

7.34 (m, IH) , 5.39-5.33 (m, IH) , 4.18-4.10 (m, IH) , 3.96-3.90 (m, IH) . Given below are formulation examples in which the parts refers to parts by weight. Formulation example 1 (Emulsifiable concentrate)

10 parts of each compound of the invention was dissolved in 45 parts of Solvesso^® 150 and 35 parts of N- methylpyrrolidone . 10 parts of emulsifier (trade name: Sorpol^® 3005X, manufactured by Toho Kagaku Co., Ltd.) was added thereto. These ingredients were mixed while stirring, thereby producing a 10% emulsifiable concentrate.

Formulation example 2 (Wettable powder)

20 parts of each compound of the invention was added to the mixture of 2 parts of sodium lauryl sulfate, 4 parts of sodium lignin sulfonate, 20 parts of fine powders of water- containing synthetic silicon oxide and 54 parts of clay. These ingredients were mixed while stirring by a juice mixer, thereby producing 20% wettable powders.

;

Formulation example 3 (Granule)

5 parts of each compound of the invention was mixed with 2 parts of sodium dodecylbenzenesulfonate, 10 parts of bentonite and 83 parts of clay, followed by thorough

agitation. A suitable amount of water was added, and the mixture was further stirred. The mixture was granulated by a granulator and air-dried, producing 5% granules.

Formulation example 4 (Dust)

1 part of each compound of the invention was dissolved in a suitable amount of acetone. To the solution were added 5 parts of the fine powders of water-containing synthetic silicon oxide, 0.3 parts of acidic isopropyl phosphate (PAP) and 93.7 parts of clay, followed by mixing and stirring by a juice mixer. Acetone was removed therefrom by evaporation, producing a 1% powder formulation.

Formulation example 5 (Flowable preparation)

20 parts of each compound of the invention was mixed with 20 parts of water-containing 3 parts of

polyoxyethylenetristyrylphenyl ether phosphoric acid and triethanolamine and 0.2 parts of Rhodorsxl^® 426R (manufactured by RhodiaChimie ) . The mixture was pulverized by a mill (trade name: DYNO-Mill, and manufactured by Willy A. Bachofen AG) using a ;wet method, and further mixed with 60 parts of water- containing 8 parts of propylene glycol and 0.32 parts of xanthan gum, thereby producing a 20% suspension in water.

Test examples are given below to demonstrate that the compounds of the invention are useful as an active ingredient for fungicides.

Test example 1 (Fungicidal test on Botrytis cinerea)

The solution of the compound of the invention (500 ppm and 200 ppm) was sprayed on fresh healthy cucumber plant at least at the three leaf stage. The cotyledon of the treated plant was cut, and its leaf was put on moist tissue paper on plastic tray. 50 μΐ of spore suspension (1 x 10⁶ cfu spore per ml) was dropped on the middle of the leaf using micropipette . And then a small disc of absorbent cotton was put on the spore drop, and again the 50 μΐ of spore suspension was dropped on the disc. Leaves were kept at room temperature (20°C) .

The radial growth of fungus after five day of inoculation was measured and the activity of the compound was shown as preventive value calculated according to the following

equation. Preventive value (%) = {1- (radial growth on treated) / (radial growth on control) } x 100.

The compounds that exhibited the preventive value of 50% or more at a treatment concentration of 500 ppm are as

follows :

Compound nos. : lc-1, lc-2H, lc-2L, lc-3, lc-3H, lc-3L, lc-4H, lc-4L, lc-5L, lc-6L, lc-8, lc-8H, lc-8L, lc-9, lc-9H, lc-9L, lc-lOH, lc-lOL, lc-HH, lc-HL, lc-13H, lc-13L, lc-14H, lc-15H, lc-16, lc-16H, lc-19, lc-20, lc-23, lc-23H, lc-23L, lc-24, lc-24H, lc-25H, lc-25L, lc-26, lc-26H, lc-26L, lc-27H, lc-28L, lc-29H, lc-29L, lc-30H, lc-32H, lc-32L, lc-33, lc-34H, lc-34L, lc-35, lc-35H, lc-35L, ld-lH, ld-6H, ld-6L, ld-13, ld- 17, ld-17H, ld-17L, le-3, le-7.

The compounds that exhibited the preventive value of 50% or more at a treatment concentration of 200 ppm are as

follows :

Compound nos . : lc-2H, lc-2L, lc-3, lc-3H, lc-3L, lc-4H, lc-4L, lc-5L, lc-6L, lc-8, lc-8H, lc-8L, lc-9, lc-9H, lc-9L, lc-lOH, lc-lOL, lc-HH, lc-13H, lc-13L, lc-14H, lc-15H, lc-16, lc-16H, lc-19, lc-20, lc-23, lc-23H, lc-23L, lc-24H, lc-25H, lc-25L, lc-26, lc-26H, lc-26L, lc-27H, lc-29H, lc-29L, lc-32H, lc-32L, lc-33, lc-34H, lc-34L, lc-35, lc-35H.

Test example 2 (Fungicidal test on Sphaerotheca fuliginea, cucumber )

The solution of the compound of the invention (500 ppm) was sprayed on fresh healthy two week old cucumber plants. The plants were air-dried and inoculated with freshly prepared spore suspension (1 x 10⁶ cfu spore per ml) . The inoculated plants were then placed in green house (25°C, a humidity of 60% and 16L8D) .

The disease area rate after 12 days of inoculation was measured and the activity of the compound was shown as

preventive value calculated according to the following

equation. Preventive value (%) = {1- (disease area rate on treated) / (disease area rate on control) } x 100.

The compounds that exhibited the preventive value of 50% or more are as follows:

Compound nos . : lc-1, lc-ΙΗ, lc-lL, lc-2H, lc-2L, lc-3, lc-3H, lc-3L, lc-4H, lc-4L, lc-5H, lc-5L, lc-6, lc-6H, lc-6L, lc-7H, lc-7L, lc-8, lc-8H, lc-8L, lc-9, lc-9H, lc-9L, lc-lOH, lc-lOL, lc-HH, lc-HL, lc-13H, lc-13L, lc-14H, lc-15H, lc-15L, lc-16, 1C-16H, lc-16L, lc-17H, lc-18L, lc-19H, lc-19L, lc-20, lc-21H, 1C-21L, lc-22H, lc-23, lc-23H, lc-23L, lc-25H, lc-25L, lc-26, lc-26H, lc-26L, lc-27H, lc-27L, lc-28H, lc-28L, lc-29H, lc- 29L, lc-30H, lc-30L, lc-31H, lc-31L, lc-32H, lc-32L, lc-33, lc-34H, lc-34L, lc-35, lc-35H, lc-35L, lc-36, lc-37, lc-37, lc-40H, lc-40L, lc-41H, lc-41L, ld-1, ld-ΙΗ, ld-lL, ld-12, ld- 13, ld-13L.

Test example 3 (Fungicidal test on Phytophthora infestans)

The solution of the compound of the invention (500 ppm) was sprayed on fresh healthy tomato plant at least at the three leaf stage. The plants were air-dried and inoculated with freshly prepared sporangia suspension (1 x 10⁶ cfu ; zoospore per ml) . The inoculated plants were then placed in a dew chamber (20°C and a humidity of 100%) . One day after inoculation, the plants were shifted to a thermostatic chamber (20°C, a humidity of 80%, and 16L8D) .

The disease area rate after 5 days of inoculation was measured and the activity of the compound was shown as preventive value calculated according to the following equation. Preventive value (%) = {1- (disease area rate on treated) / (disease area rate on control) } x 100.

Compound nos. : lc-1, lC-16, lc-16H, lc-16L, lc-19H.

Test example 4 (Fungicidal test on Pyricularia grisea)

The solution of the compound of the invention (500 ppm) was sprayed on fresh healthy two week old millet plants. The plants were air-dried and inoculated with freshly prepared spore suspension (1 x 10⁶ cfu spore per ml) . The inoculated plants were then placed in a dew chamber (25°C and a humidity of 100%) . One day after inoculation, the plants were shifted to a thermostatic chamber (25°C, a humidity of 80%, and

16L8D) .

The disease area rate after 5-7 days of inoculation was measured and the activity of the compound was shown as preventive value calculated according to; the following equation. Preventive val {1- (disease area rate on treated) / (disease area rate on control) } x 100.

Compound nos. : lc-1, lc-lL, lc-2H, lc-2L, lc-3, lc-3H, lc-3L, lc-4H, lc-4L, lc-5H, lc-5L, lc-6, lc-6H, lc-6L, lc-8, lc-8H, lc-8L, lc-9, lc-9H, lc-9L, lc-ΙΟΗ, lc-lOL, lc-HH, lc-llL, lc- 12, lc-12H, lc-13, lc-13H, lc-13L, lc-14H, lc-15H, lc-15L, lc- 16, lc-16H, lc-16L, lc-17H, lc-18L, lc-19, lc-19L, lc-20, lc- 21H, lc-21L, lc-23, lc-23H, lc-23L, lc-24, lc-24H, lc-25H, lc- 25L, lc-26, lc-26H, lc-26L, lc-27H, lc-30L, lc-32H, lc-32L, lc-34H, lc-34L, lc-35, lc-35H, lc-35L, lc-37, lc-37L, lc-38H, lc-38L, lc-44, lb-5L, ld-ΙΗ, ld-lL, ld-6L, ld-7, ld-7H, ld-7L, ld-8, ld-11, ld-llH, ld-HL, ld-12L, ld-15, ld-16, ld-16H, ld- 16L, ld-17, ld-17H, le-6.

(Note)

As described above, the present invention is illustrated by preferable embodiments of the present invention. However, it will be understood that the scope of the present invention should be interpreted only by the claims. It is understood that patents, patent applications and literatures cited herein are incorporated herein by reference, as if the contents thereof are specifically described herein. The present

application claims priority to Indian Patent Application No. 201711008910 filed on March 15, 2017 with the Indian Patent Office (Intellectual Property India), the entire content of which is incorporated herein by reference. Industrial Applicability The dithiolane compound of the present invention has a controlling effect against plant diseases and is useful as active ingredient of a plant control agent.

Claims

1. A dithiolane compound represented by Formula (1) :

salt or an N-oxide thereof,

wherein R¹, R² and R³ are identical or different and each represents hydrogen, halogen, Ci_₆ alkyl, Ci_₆ haloalkyl, Ci_₆ alkoxy, Ci-6 haloalkoxy, Ci-6 alkoxy Ci_₆ alkyl, Ci_6 haloalkoxy Ci-6 alkyl, C₂-6 alkenyl, C₂-e haloalkenyl, C₂-e alkynyl, C₂-6 haloalkynyl, C₃-e cycloalkyl, C3-8 cycloalkyl Ci-₆ alkyl, optionally substituted aryl, optionally substituted

Y¹ represents optionally substituted aryl, optionally substituted pyridyl, optionally substituted pyrazinyl, optionally substituted pyrimidinyl, or optionally substituted pyridazinyl ;

represents optionally substituted aryl or optionally substituted heteroaryl;

Q represents hydrogen, nitro, cyano, Ci_₆ alkyl, Ci-₆ haloalkyl, C -₈ cycloalkyl, C₃-₈ cycloalkyl Ci_₆ alkyl, C]_₆ alkylcarbonyl , Ci_₆ haloalkylcarbonyl , C₃-8 cycloalkylcarbonyl , Ci-6 alkoxycarbonyl , Ci_6 haloalkoxycarbonyl , C₃_₈ cycloalkoxycarbonyl , Ci-e alkylthio, C_:^₆ haloalkylthio, C -₈ cycloalkylthio, C₃_₈ cycloalkyl Ci_₆ alkylthio, Ci-₆ alkoxy Ci-₆ alkylthio, Ci-6 alkylsulfonyl, Ci_₆ alkylsulfinyl , Ci-₆

haloalkylsulfonyl , Ci-₆ haloalkylsulfinyl, C₃_₈

cycloalkylsulfonyl , C₃-₈ cycloalkylsulfinyl, C₃_₈ cycloalkyl C_x. alkylsulfonyl , C₃~₈ cycloalkyl Ci_₆ alkylsulfinyl, optionally substituted arylthio, optionally substituted aryl Ci_₆

alkylthio, optionally substituted arylsulfonyl , optionally substituted arylsulfinyl , optionally substituted aryl, optionally substituted heteroaryl, or optionally substituted heterocyclic group.

2. The dithiolane compound or a salt or an N-oxide thereof according to claim 1, wherein R¹, R² and R³ are identical or different and each represents hydrogen, halogen, or Ci-e alkyl.

3. The dithiolane compound or a salt or an N-oxide thereof according to claim 1 or 2, wherein R¹, R² and R³ are identical or different and each represents hydrogen or Ci_₆ alkyl .

4. The dithiolane compound or a salt or an N-oxide thereof according to any one of claims 1 to 3, wherein Y¹ is optionally substituted aryl or optionally substituted pyridyl

5. The dithiolane compound or a salt or an N-oxide thereof according to any one of claims 1 to 4, wherein Y¹ is optionally substituted pyridyl.

6. The dithiolane compound or a salt or an N-oxide thereof according to any one of claims 1 to 5, wherein Y¹ represents :

wherein the * is the point of attachment to the parent compound .

7. The dithiolane compound or a salt or an N-oxide thereof according to any one of claims 1 to 5, wherein Y¹ represents :

wherein the * is the point of attachment to the parent compound .

8. The dithiolane compound or a salt or an N-oxide thereof according to any one of claims 1 to 5, wherein Y¹ represents :

wherein the * is the point of attachment to the parent compound .

9. The dithiolane compound or a salt or an N-oxide thereof according to any one of claims 1 to 8, wherein Y² is optionally substituted aryl.

10. The dithiolane compound or a salt or an N-oxide thereof according to any one of claims 1 to 8, wherein Y² is optionally substituted heteroaryl.

11. The dithiolane compound or a salt or an N-oxide thereof according to any one of claims 1 to 8 and 10, wherein Y² is selected from the group consisting of:

the * is the point of attachment to the parent compound.

12. The dithiolane compound or a salt or an N-oxide thereof according to any one of claims 1 to 11, wherein cyano .

13. A plant disease-controlling agent containing the dithiolane compound or a salt or an N-oxide thereof according to any one of claims 1 to 12.

14. A fungicide containing the dithiolane compound or a salt or an N-oxide thereof according to any one of claims 1 to 12.