WO1996015093A1

WO1996015093A1 - Dihalopropene compounds, use thereof, and intermediates for production thereof

Info

Publication number: WO1996015093A1
Application number: PCT/JP1995/002320
Authority: WO
Inventors: Masaya Suzuki; Noriyasu Sakamoto; Toshio Nagatomi; Kimitoshi Umeda; Kazunori Tsushima
Original assignee: Sumitomo Chemical Company, Limited
Priority date: 1994-11-14
Filing date: 1995-11-14
Publication date: 1996-05-23
Also published as: AU3856795A

Abstract

A dihalopropene compound represented by the following general formula and exhibiting excellent insecticidal and miticidal effects: R1-Z-Y-OCH¿2?CH=CX2 wherein R?1¿ represents C¿1?-C10 alkyl etc.; Z represents oxygen etc.; Y represents a naphthalene residue to which Z and O are bonded at the 1- and 5-positions, respectively, etc.; and X represents chloro etc.

Description

Description Dihalob-opened pen compounds, their uses and intermediates for their production Field of the invention

The present invention relates to a dihalobopen pen compound, its use, and an intermediate for its production.

Conventional technology

Hitherto, it has been described in JP-A-48-86835 and JP-A-49-11526 that certain propene compounds can be used as an active ingredient of an insecticide.

However, these compounds are not always sufficient as an active ingredient of an insecticide in terms of insecticidal efficacy and the like.

In view of the above situation, the present inventors have conducted intensive studies to find a compound having excellent insecticidal activity, and as a result, a dihalopropene compound represented by the following general formula has excellent insecticidal and acaricidal activity. This led to the completion of the present invention.

SUMMARY OF THE INVENTION

The present invention provides a compound represented by the general formula (1):

R ¹ -ZY-OCH ₂ CH = CX ₂

[Wherein, R ¹ is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a haloalkenyl group having 2 to 6 carbon atoms, and 3 to 9 carbon atoms. Represents an alkynyl group, a haloalkyl group having 3 to 5 carbon atoms, an alkoxyalkyl group having 2 to 7 carbon atoms or an alkylthioalkyl group having 2 to 7 carbon atoms, or an alkyl having 1 to 4 carbon atoms May be substituted with an alkoxy group having 1 to 3 carbon atoms or a haloalkoxy group having 1 to 3 carbon atoms, or represents a cycloalkyl group having 3 to 6 carbon atoms, or an alkyl having 1 to 4 carbon atoms. A cycloalkylalkyl group having 4 to 9 carbon atoms which may be substituted with an alkyl group, a cycloalkenyl group having 5 to 6 carbon atoms or a cycloalkenyl group having 1 to 4 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms. T represents a cycloalkenylalkyl group having 6 to 8 carbon atoms which may be substituted with an alkyl group, or

--

Q ₇ (In the formula, A represents an optionally substituted fuunyl group, an optionally substituted naphthyl group or an optionally substituted heterocyclic group,

B represents an oxygen atom, S (0) _n group, NR ¹¹ group, C (= 0) G group or a GC (= 0) group (wherein, n represents an integer from 0 to 2, R ¹¹ is a hydrogen atom or Represents an alkyl group having 1 to 3 carbon atoms, G represents an oxygen atom or an NR ¹⁵ group, and R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

R ² , R ³ , RR ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a trifluoromethyl group,

R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a trifluoromethyl group or a halogen atom,

R ⁹ represents a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a haloalkoxy group having 1 to 3 carbon atoms,

R ^{1 ()} represents a hydrogen atom, a halogen atom or a methyl group, i represents an integer from 0 to 6, j represents an integer from 1 to 6, k represents an integer from 0 to 4, 1 (el ) Represents 1 or 2, and m represents an integer from 0 to 2. )

Represents Q, Q ₂ , Q ₃ , Q ₄ , Q ₅ , Q ₆ , h, Q ₈ or Q ₉ .

Z represents an oxygen atom, a sulfur 'atom or an NR ¹² group (where R ¹² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms).

Y is the formula: ( ³ ) P

Y _3. Y ₄ Y,

(Wherein, R ¹³ is each independently a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, an alkyl group having 2 to 4 carbon atoms or a group having 2 to 4 carbon atoms. represents 4 Haroaruke two Le group, p is in. Υ! ~Υ ₉ each structural formula which represents the integer from 0 to 3, the binding of the left one of the two bonds are assumed to be bonded to Ζ . represented _{_{by) Υ !, Υ 2, Υ 3}} , Υ 4, γ 5,

Ye Upsilon _7, represents a Upsilon ₈ or Upsilon _9.

X each independently represents a chlorine atom or a bromine atom. ]

-0- Disclosed are a halopropene compound (hereinafter, referred to as the compound of the present invention) and an insecticide and acaricide containing the compound as an effective component.

The present invention further provides a compound of the general formula (2) useful as an intermediate for producing some of the compounds of the present invention:

[Wherein, Z and X represent the same meaning as above, and Y ₁₀ represents 、,, Υ ₂ , Υ

3 or Υ represents a _4. ]

And a compound in which Y _1C is Υ, and in particular, a compound in which Z is an oxygen atom, R ¹³ is a halogen atom, and p is 0 or 1. I do.

Detailed description of the invention

In the compound of the present invention, A represents, as an embodiment of A, a phenyl group which may be substituted with (R ¹⁴ ) _q or a naphthyl group which may be substituted with (R ¹⁴ ), or an oxygen atom, a zeo atom or comprising at least 1 pc a奎素atoms, including at least 1 Ke and (R ¹ ⁴⁾ or represents an optionally substituted 6-membered heterocyclic ring group _q, or an oxygen atom, I O © atom or a nitrogen atom, (R ¹⁴ ). Represents a 5-membered heterocyclic group which may be substituted. Here, q represents an integer of 0 to 7, R ¹⁴ is a halogen atom, a cyano group, a nitro group, an (alkoxy having 1 to 4 carbon atoms) carbonyl group, an alkyl group having 1 to 8 carbon atoms, Haloalkyl group having 1 to 3 carbon atoms, alkoxy group having 1 to 7 carbon atoms, haloalkoxy group having 1 to 3 carbon atoms, alkylthio group having 1 to 3 carbon atoms, haloalkylthio group having 1 to 3 carbon atoms, 1 to 2 carbon atoms Alkylsulfinyl group having 1 to 2 carbon atoms, haloalkylsulfinyl group having 1 to 2 carbon atoms, haloalkylsulfonyl group having 1 to 2 carbon atoms, alkenyloxy group having 3 to 6 carbon atoms, carbon number 3 From 6 to 6 haloalkenyloxy groups, alkenyl with 2 to 4 carbon atoms Group, haloalkenyl group having 2 to 4 carbon atoms, alkynyl group having 2 to 4 carbon atoms, haloalkynyl group having 2 to 4 carbon atoms, alkynyloxy group having 3 to 6 carbon atoms, halo having 3 to 6 carbon atoms Alkynyloxy group, alkoxyalkyl group having 2 to 4 carbon atoms, alkylthioalkyl group having 2 to 4 carbon atoms, amino group, dimethylamino group, acetoamide group, acetyl group, haloacetyl group, formyl group, carboxyl group, ( An alkyl) aminocarbonyl group having 1 to 2 carbon atoms, a [di (alkyl having 1 to 2 carbon atoms) amino] carbonyl group, a cycloalkyl group having 3 to 6 carbon atoms, a cycloalkenyl group having 5 to 6 carbon atoms, Represents a cycloalkyloxy group having 3 to 6 carbon atoms or a cycloalkenyloxy group having 5 to 6 carbon atoms, or is a halogen atom or 1 to 4 carbon atoms, respectively. An alkyl group, a haloalkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a haloalkoxy group having 1 to 3 carbon atoms, which may be substituted with a phenyl group, a phenoquine group, a benzyl group or a benzyloxy group. Or when Q is 2 to 5, two adjacent R ¹⁴ are bonded to each other at the terminal to represent a trimethylene group, a tetramethylene group, a methylenedioxy group or an ethylenedioxy group. ].

In the compound of the present invention, the alkyl group having 1 to 10 carbon atoms represented by R ¹ includes, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group. —Butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, heptyl, 1-ethylpropyl, 1,1-dimethylhexyl, 1-methylbutyl, 2-methylbutyl, 1, 2-dimethylpropyl group, isohexyl group, 1-methylpentyl group, 2-ethylbutyl group, octyl group, 1-methylheptyl group, 1-methyloctyl group, nonyl group, decyl group, etc. The haloalkyl group having 1 to 5 carbon atoms represented by R ¹ includes, for example, a trifluoromethyl group, a difluoromethyl group, a bromodifluoromethyl group,

2.2-Trifluoroethyl, 2-Fluoroethyl, 2-Chloroethyl, 2-Bromoethyl, 1-Fluoroethyl, 1-Chloroethyl, 1-Bromoethyl, 3,3,3,2,2 —Pentafluorov mouth pill group, 3,

3,3-trifluoropropyl group, 1-fluoropropyl group, 2-chloropropyl group, 3-bromopropyl group, 1,1,2,2,2-pentafluorofluoroethyl group, 2-odoethyl group, 2 1,2-Dichloromethyl, 2-bromo-1,1,2,2-tetrafluoroethyl, 1,1,2,2-tetrafluoroethyl, 2-chloro-1,1,2-trifluoro Loethyl group, 2-bromo-1,2.2-trifluoroethyl group, 2,2,2-trichloroethyl group, 2,2,

2-tribromoethyl group, 3-fluoropropyl group, 3-chloropropyl group, 3-iodopropyl group, 1,1,2,3,3,3-hexafluoropropyl group, 2,3-dibumopropyl Group, 2,2.3,3-tetrafluoropropyl group, 2-chloro-1-methylethyl group, 2-bromo-11-methylethyl group, 2-fluoro-11- (fluoromethyl) ethyl group, 2-bromo-11- (bromomethyl) group Ethyl group, 2-chloro-11- (chloromethyl) ethyl group, 2,2,2-trifluoro-11- (trifluoromethyl) ethyl group, 4-fluorobutyl group, 4-chlorobutyl group, 4-bromobutyl group, 4-iodobutyl group, 2- (bromomethyl) propyl group, 2,2,3,4,4.4-hexafluorobutyl group, 3-promo 11- (bromomethyl) propyl group, 2-chloro-2-methylpropyl group, Five Fluoropentyl, 5-chloropentyl, 5-bromopentyl, 5-odopentyl, 3-chloro-2,2-dimethylpropyl, 3-promo 2,2-dimethylpropyl, 2.2, 3, 3, 4 , 4, 5, 5—octafluoropentyl group, etc. The alkenyl group having 2 to 10 carbon atoms represented by R ¹ includes, for example, a vinyl group, an aryl group, an isopropyl group, a 2-butenyl group, a 3-butenyl group, a 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, 2-pentenyl group, 1-methyl-2-butenyl group, 2-methyl-2-butenyl group, 3-methyl-2-butenyl group, 1-ethyl-2-propenyl group, 2- Ethyl-2-propenyl group, 1-methyl-3-butenyl group, 2-methyl-3-butenyl group, 3-methyl-3-butenyl group, 2-hexenyl group, 3-hexenyl group, 4-1 Xenyl, 5-hexenyl, 2-methyl-2-pentenyl, 1,3-dimethyl-2-butenyl, 1-methyl-4-pentenyl, 1-ethyl-2-butenyl, 2-ethyl-2- Butenyl, 1-vinylbutyl, 2-isopropyl 2-propenyl group, 2-heptenyl group, 1-aryl-3-butenyl group, 1-vinylhexyl group, 1,5-dimethyl-4-hexenyl group, 3-nonenyl group, 3- Decenyl group, 3,7-dimethyl-6-octenyl group, etc.

The haloalkenyl group having 2 to 6 carbon atoms represented by R ¹ includes, for example, 2,2-dichloroethenyl group, 2,2-dibromoethenyl group, 3,3-dichloro-1--2-propenyl group, 3.3-dibromo-12-propenyl group, 2,3-dichloro-12-probenyl group, 2,3-dibut-2-amine 2-propenyl group, 2-chloro-2-propenyl group , 3-chloro-2-propenyl group, 2-bromo-

2-propenyl group, 3-chloro-2-butenyl group, 2-chloroethenyl group,

3-bromo-2-propenyl group, 3,3-difluoro-2-propenyl group, 4-chloro-2-butenyl group, 4.4,4-trifluoro-2-butenyl group, 2- (chloromethyl) 1-2 —Propenyl group, 3-chloro-4,4,4-trifluoro-2-butenyl group, 4-bromo-3,4,4-trifluoro-2-butenyl group, 3,4,4,4-tetrafluoro-2 —Butenyl group, 4,4 zig 1,4-butenyl group, 4,4-dibutene 3-butenyl group, 6,6-dichloro-5-hexenyl group, etc.

The alkynyl group having 3 to 9 carbon atoms represented by R ¹ includes, for example, 2-propynyl group, 2-butynyl group, 3-butynyl group, 1-methyl-2-propynyl group, 2-pentynyl group Group, 3-pentynyl group, 4-pentynyl group, 1-methyl-3-butynyl group, 2-methyl-3-butynyl group, 1-ethyl-2-propynyl group, 2-hexynyl group, 3-hexynyl group , 2-heptinyl group, 3-butynyl group, 1-ethynylhexyl group, 3-noninyl group, 5-hexynyl group, etc.

The haloalkynyl group having 3 to 5 carbon atoms represented by R ¹ is, for example, 3 —cyclo—2-propynyl group, 3-bromo-2-propynyl group, 3-iodo-2-propynyl group, 1-methyl-3 —Chloro-2-propynyl group, 1-methyl-3-promo-2-propynyl group, 1-methyl-13-ododo-2-propynyl group, 4-chloro-2-butynyl group, 4-chloro-3-butynyl group, 4— Bromo-3-butynyl, 5-chloro- 4-pentynyl, 5-bromo- 4-pentynyl, 4-chloro-2-methyl-3-butynyl, 4-bromo-2-methyl-3-butynyl, 4-chloro-1-methyl One 3-butynyl group, 4-bromo-1-methyl-3-butynyl group, 3-chloro-

1-ethyl-2-propynyl group, 3-bromo-1-ethyl-2-propynyl group, etc.

The alkoxyalkyl group having 2 to 7 carbon atoms represented by R ¹ includes, for example, a methoxymethyl group, an ethoxyquinmethyl group, a propyloxymethyl group, an isopropylpyroxymethyl group, a 2-methoxethyl group, a 1-methoxyl group,

2-ethoxyquinethyl group, 1-ethoxyquinethyl group, 3-methoxypropyl group, 2-methoxypropyl group, 1-methoxypropyl group, 2-methoxyethoxy Methylethyl group, 2-propyloxyethyl group, 2-isopropyloxyethyl group, 2-ethoxy-2-methylethyl group, 2-ethoxy-1-methylethyl group, 2-methoxybutyl group, 1-ethyl-2-methyloxyethyl group, 3-ethoxypropyl group, 3-methoxybutyl group, 3-methoxy-2-methylpropyl group, 3-methoxy-1-methylpropyl group, 2-butoxyethyl group, 3-methoxy-3-methylbutyl group, 2-butoxy 1 is a monomethylethyl group, etc.

Examples of the alkylthioalkyl group having 2 to 7 carbon atoms represented by R ¹ include a methylthiomethyl group, an ethylthiomethyl group, a propylthiomethyl group, an isopropylthiomethyl group, a 2-methylthioethyl group, a 1-methylthioethyl group, 2-ethylthioethyl group, 1-ethylthioethyl group, 3-methylthiopropyl group, 2-methylthiopropyl group, 1-methylthiopropyl group, 2-methylthio-1-methylethyl group, 2-propylthioethyl group, 2 — Isopropylthioethyl group, 2-ethylthiopropyl group, 2-ethylthio-11-methylethyl group, 2-methylthiobutyl group, 1-ethyl-2-methylthioethyl group, 3-ethylthiopropyl group, 3-methylthiobutyl Group, 2-methyl-3-methylthiopropyl group, 1-methyl-3-methylthiopropyl group, 4-methyl Ruthiobutyl group, 1-methyl-2-methylthiopropyl group, 2-tert-butylthioethyl group, 2-isobutylthioethyl group, 21 sec-butylthioethyl group, 3-tert-butylthiopropyl group, 3-isobutylthio Propyl group, 3-sec-butylthiopropyl group, etc.

In the alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms which may be substituted by a haloalkoxy group having 1 to 3 carbon atoms represented by R ¹ And an alkyl group having 1 to 4 carbon atoms means a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Butyl, sec-butyl or tert-butyl,

An alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms which may be substituted with a haloalkoxy group having 1 to 3 carbon atoms represented by R ¹ In the above, the alkoxy group having 1 to 3 carbon atoms is a methoxy group, an ethoxy group, a propoxy group or an isopropoxy group,

R ¹ represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms which may be substituted with a haloalkoxy group having 1 to 3 carbon atoms. The haloalkoxy group having 1 to 3 carbon atoms is, for example, a trifluoromethoxine group, a difluoromethoxy group, a bromodifluoromethoxy group, a 2,2.2-trifluorofluorethoxy group, a 2,2,2,1 1-pentafluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-chloro-1,1,2, -trifluoroethoxy, 2-bromo-1,1,2-trifluoroethoxy A 1,1,2,2-tetrafluoroethoxy group, a 3,3,3,2.2,1-hexafluoropropoquine group, and the like;

In the alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms which may be substituted by a haloalkoxy group having 1 to 3 carbon atoms represented by R ¹ The cycloalkyl group having 3 to 6 carbon atoms is a cyclopropyl group, a cyclobutyl group, a cyclopentyl group or a cyclohexyl group,

In the cycloalkylalkyl group having 4 to 9 carbon atoms which may be substituted by the alkyl group having 1 to 4 carbon atoms represented by R ¹ , the alkyl group having 1 to 4 carbon atoms means a methyl group, an ethyl group, Propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl; The cycloalkylalkyl group having 4 to 9 carbon atoms in the cycloalkylalkyl group having 4 to 9 carbon atoms L which may be substituted with an alkyl group having 1 to 4 carbon atoms represented by R ¹ is, for example, cycloalkyl Propylmethyl group, 1-cyclopropylpropyl group, 2-cyclopropylethyl group, cyclobutylmethyl group, cyclopentylmethyl group, 2-cyclopentylethyl group, 3-cyclopentylpropyl group, cyclohexylmethyl group, 2-cyclohexyl A xylethyl group, a 3-cyclohexylpropyl group, etc.

It may also be substituted with one carbon atoms represented by R ¹ in 4 alkyl t, in cycloalkenyl group having 5 to 6 carbon atoms, the alkyl group having 1 to 4 carbon atoms, a methyl group, Echiru group, Propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl;

The cycloalkenyl group having 5 to 6 carbon atoms in the cycloalkenyl group having 5 to 6 carbon atoms which may be substituted with the alkyl group having 1 to 4 carbon atoms represented by R ¹ is a 1-cyclopentenyl group, 2 —Cyclopentenyl, 3-cyclopentenyl, 1-cyclohexenyl, 2-cyclohexenyl, or 3-cyclohexenyl;

In cycloalk 'Keniruarukiru group having carbon atoms 6 be substituted with an alkyl group having from 1 to 4 carbon atoms represented by R ¹ 8, the Al kill group having 1 to 4 carbon atoms, a methyl group, Echiru group, Propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl;

The cycloalkenylalkyl group having 6 to 8 carbon atoms in the cycloalkenylalkyl group having 6 to 8 carbon atoms which may be substituted by the alkyl group having 1 to 4 carbon atoms represented by R ¹ is, for example, 1- Cyclopentenylmethyl group,

2-cyclopentenylmethyl group, 3-cyclopentenylmethyl group, 1-cyclohexenylmethyl group, 2-cyclohexenylmethyl group, 3-cyclohexane A xenylmethyl group, a 2- (3-cyclohexenyl) ethyl group,

The halogen atom represented by R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹³ and R ¹⁴ is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom,

The alkyl group having a carbon purple number of 1 to 4 represented by R ⁹ and R ¹³ is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group or a tert-butyl group. ,

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ¹⁴ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, Isopentyl group, neopentyl group, tert-pentyl group, hexyl group, heptyl group, 1,1-dimethylhexyl group, 1-methylbutyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, isohexyl group , A 1-methylpentyl group, a 2-ethylbutyl group, an octyl group, a 1-methylhexylbutyl group, etc.

The haloalkyl group having 1 to 3 carbon atoms represented by R ⁹ , R ¹³ and R ¹⁴ includes, for example, trifluoromethyl group, trichloromethyl group, difluoromethyl group, bromodifluoromethyl group, 2,2,2 2-trifluoroethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, 1-fluoroethyl group, 1-chloroethyl group, 1-bromoethyl group, 3, 3, 3, 2 1,2-pentafluoropropyl group, 3,3,3-trifluoropropyl group, 11-fluoropropyl pill group, 2-chlorobu pill group, 3-bromopropyl group, etc.

The alkoxy group having 1 to 3 carbon atoms represented by R ⁹ is a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group,

The haloalkoxy group having 1 to 3 carbon atoms represented by R ⁹ and R ¹⁴ is, for example, a trifluoromethoxy group, a difluoromethoxy group, a bromodifluo group. Fluoromethoxy, 2-fluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-chloro1.1,2-trifluoroethoxy, 2-bromo-1 1.1, 2—Trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 3,3,3,2,1,1-hexafluorobromoboxyl, 3-fluoropropoxy Group, 3-chloropropoxy group, 3-bromopropoxy group, 3,3,3,2,2-pentaphenylopropyl group, 3,3,3-trifluoropropoxy group, 2,2,2 1,1-pentafluoroethoxy group, 3,3,3,2,1,1 hexafluorob or oxy group, etc.

The alkyl group having 1 to 3 carbon atoms represented by R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹¹ , R ¹² and R ¹⁵ is a methyl group, an ethyl group, Propyl or isopropyl;

The alkoxy group having 1 to 7 carbon atoms represented by R ¹⁴ is, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, Pentyloxy, isopentyloxy, 1-methylbutyne, 1-ethylpropoxy, neopentyloxy, tert-pentyloxy, 1,2-dimethylpropoxy, hexyloxy, heptyloxy, etc. ,

The alkylthio group having 1 to 3 carbon atoms represented by R ¹⁴ is a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group,

The haloalkylthio group having 1 to 3 carbon atoms represented by R ¹⁴ includes, for example, trifluoromethylthio group, difluoromethylthio group, bromodifluoromethylthio group, 2.2,2-trifluoroethylthio group, 2-chloro- 1,1,2-Trifluoroethylthio group, 2-Bromo-1,1.2-Trifluoroethylthio group, 1,1,2.2-Tetrafluoroethylthio group, 2-chloro Roethylthio, 2-fluoroethylthio, 2-bromoethylthio, 1,1,2,2,2-pentafluoroethylthio, 3-fluoropropylthio, 3-chloropropyl Thio group, 3-bromopropylthio group, 3,3.3,2,2-pentafluoropropylthio group, 3,3,3-trifluoropropylthio group, etc.

The alkenyloxy group having 3 to 6 carbon atoms represented by R ¹⁴ includes, for example, an aryloxy group, a 2-methyl-2-propenyloxy group, a 1-methyl-2-propenyloxy group, a 2-butenyloxy group, a 3-butenyloxy group, A methyl-2-butenyloxy group, a 2-methyl-2-butenyloxy group, a 2-pentenyloxy group, a 2-hexenyloxy group, etc.

Examples of the haloalkenyloxy group having 3 to 6 carbon atoms represented by R ¹⁴ include, for example, 3,3-dichloro-2-propenyloxy group, 3,3-dibutene 2-phenylpropoxy group, 2.3 —Dichloro-2-propenyloxy group, 2,3-diphenyl 2-, propenyloxy group, 2-chloro-2-propenyloxy group, 3-chloro-2-propenyloxy group, 2-bromo-2-pro Phenyloxy group, 3-fluoro-3-chloro-2-propenyloxy group, 3-methyl-4,4,4-trifluoro-2-butenyloxy group, 3-chloro-2-butenyloxy group, etc.

The alkenyl group having 2 to 4 carbon atoms represented by R ¹³ and R ¹⁴ is, for example, a vinyl group, an isopropyl group, a 1-propyl group, a 2-methyl-11-propyl group, a 1-methyl group. 1-Propenyl group, aryl group, 1-methyl-

2-propenyl group, 2-butenyl group, etc.

The haloalkenyl group having 2 to 4 carbon atoms represented by R ¹³ and R ¹⁴ is, for example, 2,2-dichloroethenyl group, 2,2-dibromoethenyl group, 3,3

3-dichloro-2-propenyl group, 3,3-dibutene 2-propenyl group, 2,3-dichloro-2-propenyl group, 2,3-dibutene 2-propenyl group, 2-chloro-2-propenyl group, 3-chloro-2-propenyl group, 2-promo-2 —Propenyl group, 3-chloro-2-butenyl group, etc.

The alkynyl group having 2 to 4 carbon atoms represented by R ¹⁴ is, for example, ethynyl group, 1-propynyl group, 2-propynyl group, 1-methyl-2-propynyl group,

The haloalkynyl group having 2 to 4 carbon atoms represented by R ¹⁴ includes, for example, a chloroethynyl group, a bromoethynyl group, an odoethynyl group, a 3-chloro-2-propynyl group, a 3-promo-2-propynyl group, and a 3-propynyl group. —Odo-2-propynyl group, 1-methyl-3-chloro-2-propynyl group, 1-methyl-3-bromo-2-propynyl group, 1-methyl-3-propynyl 2-propynyl group, etc.

The alkoxyalkyl group having 2 to 4 carbon atoms represented by R ¹⁴ includes, for example, methoxymethyl group, ethoxymethyl group, propyloxymethyl group, isopropyl pyroxymethyl group, 2-methoxethyl group, and 1-methyl group. Toxityl group, 2-ethoxyethoxyl group, 1-ethoxyquinethyl group, 3-methoxypropyl group, 2-methoxypropyl group, 1-methoxypropyl group, 2-methoxy-11-methylethyl group,

The alkylthioalkyl group having 2 to 4 carbon atoms represented by R ¹⁴ includes, for example, methylthiomethyl group, ethylthiomethyl group, propylthiomethyl group, isopropylthiomethyl group, 2-methylthioethyl group, 1-methylthioethyl group Group, 2-ethylthioethyl group, 1-ethylthioethyl group, 3-methylthiopropyl group, 2-methylthiopropyl group, 1-methylthiopropyl group, 2-methylthio-1-methylethyl group, etc.

The cycloalkyl group having 3 to 6 carbon atoms represented by R ¹⁴ is, for example, Chloropropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.

The cycloalkenyl group having a carbon violet number of 5 to 6 represented by R ¹⁴ is, for example, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-cyclohexenyl group, 2-cyclopentyl group, Hexenyl group, 3-cyclohexenyl group, etc.

The cycloalkyloxy group having 3 to 6 carbon atoms represented by R ¹⁴ is, for example, a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, etc.

Examples of the cycloalkenyloxy group having 5 to 6 carbon atoms represented by R ¹⁴ include a 1-cyclopentenyloxy group, a 2-cyclopentenyloxy group, a 3-cyclopentenyloxy group, and a 1-cyclopentyloxy group. Hexenyloxy, 2-cyclohexenyloxy, 3-cyclohexenyloxy, etc.

The alkylsulfinyl group having 1 to 2 carbon atoms represented by R ¹⁴ is a methylsulfinyl group or an ethylsulfinyl group,

The alkylsulfonyl group having 1 to 2 carbon atoms represented by R ¹⁴ is a methylsulfonyl group or an ethylsulfonyl group,

The haloalkylsulfinyl group having 1 to 2 carbon atoms represented by R ¹⁴ includes, for example, trifluoromethylsulfinyl group, 2,2,2-trifluoroethylsulfinyl group, perfluoroethylsulfinyl group, and the like And

Examples of the haloalkylsulfonyl group having 1 to 2 carbon atoms represented by R ¹⁴ include a trifluoromethylsulfonyl group, a 2,2,2-trifluoroethylsulfonyl group, a perfluoroethylsulfonyl group, and the like. And

The (amino having 1 to 2 carbon atoms) aminocarbonyl group represented by R ¹⁴ is a methylaminocarbonyl group or an ethylaminocarbonyl group, The [di (alkynole) amino] carbon atom represented by R ¹⁴ is a dimethylaminocarbonyl group, an N-methyl-N-ethylaminocarbonyl group, a acetylaminocarbonyl group, or the like,

R "represents a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a haloalkoxy group having 1 to 3 carbon atoms, respectively. An alkyl group having 1 to 4 carbon atoms in a phenyl group, a phenoxy group, a benzyl group or a benzyloxy group which may be substituted with: a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group , Tert-butyl or isobutyl,

A halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a haloalkoxy having 1 to 3 carbon atoms, each represented by R ¹⁴ A haloalkyl group having 1 to 3 carbon atoms in a phenyl group, a phenoxy group, a benzyl group or a benzyloxy group which may be substituted with a group is, for example, a trifluoromethyl group, a difluoromethyl group, a bromodifluoromethyl group , 2,2—difluoroethyl group, 2,

2.2 2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 1-fluoroethyl, 1-chloroethyl, 1-bromoethyl, 3, 3, 3, 2 2-pentafluoropropyl group, 3.

3,3-trifluoropropyl group, 1-fluoropropyl group, 2-chloropropyl group, 3-bromopropyl group, etc.

A halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a haloalkoxy having 1 to 3 carbon atoms, each represented by R ¹⁴ An alkoxy group having 1 to 3 carbon atoms in a phenyl group, a phenoxy group, a benzyl group or a benzyloxy group which may be substituted with a methoxy group, an ethoxy group, a propoxy group or a methoxy group. A sopropoxy group,

A halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a haloalkoxy group having 1 to 3 carbon atoms, each represented by R ¹⁴ A haloalkoxy group having 1 to 3 carbon atoms in a phenyl group, a phenoxy group, a benzyl group or a benzyloxy group, which may be substituted with, for example, a trifluoromethyloxy group, a difluoromethoxy group, a bromodifluoromethoxy group , 2-fluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-chloro-1,1,2-trifluoroethoxy, 2- Promo 1,1,2—Trifluoroethoxy group, 1,1,2,2-Tetrafluoroethoxy group, 3,3,3,2,2.1—Hexafluoropropoxy group, 3-Fluoropropoxy group Base 3-chloropropoxy group, 3-bromopropoxy group, 3,3,3,2,2-fluoropropoxy group, 3,3.3-trifluoropropoxy group, 2.2.2.1, 1-pentafluoroethoxy And the like.

The heterocyclic ring in the heterocyclic group which may be substituted represented by A is, for example, isooxazole, isothiazole, thiazole, 1,3,4-thiadiazole, pyrrole, furan, thiophene, pyrazole, imidazole, 2,3-triazole, 1,2,4-triazole, 1.2,3,4-tetrazole, pyridine, pyridazine, pyrimidine, pyrazine, 1,2.4-triazine, 1,3,5-triazine, Indole, benzofuran, thianaphthalene, indazole, benzimidazole, benzotriazole, benzisoxazole, benzoxazole, benzothiazole, quinoline, isoquinoline, quinoxaline, quinazole, pyridin, pyrazine, tetrahydrofuran , Tetrahydrobiran, virazoline and the like.

In the compound of the present invention, In a preferred embodiment of R ^1,

R ¹ is Q, and A is (R ¹⁴ ). A phenyl group optionally substituted with or a 2-pyridyl group optionally substituted with (R ") _q :

In R ¹ is Q _2, and, A is (R ¹⁴⁾ which may be substituted with Fuyuniru group, (optionally substituted with R 2-pyridyl group or (R ^14), in but it may also be substituted Compounds that are 3-pyridyl groups;

R ¹ is Q ₃ , and an A group, a phenyl group optionally substituted with (R) _q , a 2-pyridyl group optionally substituted with (R ″) or (R ¹⁴ ) A compound that is a 3-pyridyl group;

R ¹ is Q ₄ , Q ₅ , Q ₆ , Q ₇ , Q ₈ or Q ₉ , and is a phenyl group optionally substituted with (R ¹⁴ ); substituted with (R ¹⁴ ) _q A compound which is a 2-pyridyl group or a 3-pyridyl group optionally substituted with (R ¹⁴ ) _q ;

Preferred embodiments of Z include an acid atom,

Preferred embodiments of Y include Y,

A preferred embodiment of (R ¹³ ) p is a compound wherein R ¹³ is a halogen atom, and p is 0 or 1.

In a preferred embodiment of B, oxygen atom, C0 ₂ group or CONH group.

In the compound of the present invention, preferred compounds are

Y is Y, R ¹ is Q, and A is a phenyl group or (R ¹⁴ ) optionally substituted with (R ¹⁴ ) _Q. A 2-pyridyl group optionally substituted with: Z is an oxygen atom; R ¹³ is a halogen atom; and p is 0 or 1;

Y is Y, R ¹ is Q ₂ , and A is (R ¹⁴ ) _Q A 2-pyridyl group or a 3-pyridyl group optionally substituted with (R ¹⁴ ) _q , wherein Z is an oxygen atom, and R ² , R ³ and R ⁴ are A compound which is a hydrogen atom, i is an integer of 0 to 3, R ¹³ is a halogen atom, and p is 0 or 1;

Y is not less, R ¹ is Q _3, A is substituted with (R ¹⁴⁾ may be substituted by _Q Hue group, in which may be substituted 2-pyridyl group, or (R ") _q A 3-pyridyl group, Z is an oxygen atom, and B is an oxygen atom, a group of 0 ₂ or a group of 0 ^^ 1 ^, and R ² , R ³ and R ⁴ is water atom, and i is 2 or 3, and, R ¹³ is a halogen atom, and compound p is 0 or 1 and the like.

The compound of the present invention can be produced, for example, by the following methods (Production method A) to (Production method I).

(Production method A)

When R ¹ is other than C, Z is an oxygen atom, and Y is Y ,, Υ ₂ , Υ ₃ or Υ ₄ , that is, Υ is ₁₀ , the general formula (3):

R ¹ - 0Η

[Wherein, R ¹ has the same meaning as described above. ]

Al? Compounds and the general formula (4):

HO- Y, ₀ -OCH ₂ CH = CX ₂

[Wherein, Y _{1 ()} and X represent the same meaning as described above. ]

A method for producing a compound represented by the formula:

The above reaction is preferably carried out in the presence of a suitable dehydrating agent, if necessary, in an inert solvent. Examples of the dehydrating agent used include dicyclohexyl carbodiimidodialkyl (eg, d—C ₄ ) azodicarboxylate (diethyl azodicarboxylate, diisopropyl azodicarboxylate). Rate Etc.) Trialkyl (eg, d—C ₂ c) phosphine or triarylphosphine (triphenylphosphine, trioctylphosphine, tributylphosphine, etc.) type.

Examples of the solvent used include hydrocarbons such as benzene, xylene, and toluene; ethers such as dimethyl ether, diisopropyl ether, tetrahydrofuran, and dioxane; and carbon tetrachloride, dichloromethane, and benzene. Halogenated hydrocarbons such as dichlorobenzene can be mentioned.

The reaction temperature can range from 20 ° C to 200 ° C or the boiling point of the solvent used in the reaction.

The molar ratio of the raw materials and the dehydrating agent to be used for the reaction can be set arbitrarily, but it is advantageous to carry out the reaction in an equimolar or close ratio.

After completion of the reaction, the reaction solution can be subjected to ordinary post-treatments such as extraction with an organic solvent, kanshu, etc. to isolate the target compound of the present invention. If necessary, it can be further purified by conventional procedures such as chromatography, distillation, recrystallization, etc.

(Production method B)

General formula (5):

R ^1-

[Wherein, R ¹ has the same meaning as described above, and L ¹ represents a halogen atom (a chlorine atom, a bromine atom, an iodine atom, etc.), a mesyloxy group or a tosyloxy group. And a general formula (6): HZY-OCH

2 then Π = Λ 2

[Wherein, Z, Y and X represent the same meaning as described above. ]

A method for producing a compound represented by the formula: The above reaction is preferably performed in an inert solvent in the presence of a suitable base. As the solvent used, ketones such as acetone and key Sanon methyl E chill ketone, cyclohexane, 1. 2-dimethyl Tokishietan, as tetrahydrofuran, Jiokisan, dialkyl (e.g., d-C ₄₎ ether (e.g., Jechiruete Le , Diisopropyl ether, etc.), polar solvents such as N, N-dimethylformamide, dimethylsulfoxide, hexamethylphosphoric triamide, sulfolane, acetonitrile, nitromethane, etc .; dichloromethane, chlorophonolem, 1,2-dichloroethane, chloroform Examples thereof include hydrocarbons such as lip benzene, hydrocarbons such as toluene, benzene, and xylene, and water. If necessary, a mixed solvent of these solvents can be used.

Examples of the base used include lithium hydroxide, sodium hydroxide, potassium hydroxide, hydroxide of alkali metal or alkaline earth metal such as calcium hydroxide, lithium carbonate, lithium carbonate, sodium carbonate, Alkali metal or alkaline earth metal such as calcium carbonate, alkaline hydride, lithium hydride, sodium hydride, alkaline hydride, calcium hydride, etc.Alkali metal or alkaline earth metal metal hydride, sodium main Tokishido, sodium Muetokindo, Al force Li metal alkoxides such as Riumu tert- butoxide (e.g., C! one C _4), Bok Riechiruamin, organic bases such like et be such as pyridine. If necessary, a catalyst such as an ammonium salt (eg, triethylbenzylammonium chloride) may be added to the reaction system in an amount of 0.01 to 1 mol based on 1 mol of the compound represented by the above general formula (6). You may add in proportion.

The reaction temperature can usually range from 150 ° C. to the boiling point of the solvent used in the reaction or 150 ° C., but from 150 ° C. to the boiling point of the solvent used in the reaction or 100 ° C. Temperatures up to ° C are more desirable. The molar ratio of the starting material and the base to be used for the reaction can be arbitrarily set, but it is advantageous to carry out the reaction in an equimolar or close ratio.

After completion of the reaction, the reaction solution is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration to isolate the target compound of the present invention. If necessary, it can be further purified by usual procedures such as chromatography, distillation and recrystallization.

(Production method C)

—General formula (7): 2 5

R'-Z- Y-OH

Wherein, RZ and Y _c represent the same meanings as described above]

And a compound represented by the general formula (8):

L ^I -CH ₂ CH = CX ₂

[Wherein, X and L ¹ represent the same meaning as described above. ]

And a halide compound represented by the following formula: The above reaction is preferably performed in an inert solvent in the presence of a suitable base. Solvents used include ketones such as acetone, methyl ethyl ketone and cyclohexanone, 1,2-dimethoxetane, tetrahydrofuran, dioxane, and dialkyl (eg, C, 1 C ₄ ) ether (eg, , NN-dimethylformamide, dimethylsulfoxide, hexamethylphosphoric acid triamide, sulfolane, acetonitrile, nitromethane, etc., polar solvents such as dichloromethane, chloroform, 1,2-dichloroethane And halogenated hydrocarbons such as benzene, and hydrocarbons such as toluene, benzene and xylene, and water. If necessary, use a mixture of these solvents be able to.

Examples of the base to be used include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and other alkali metal or alkaline earth metal hydroxides, lithium carbonate, potassium carbonate, sodium carbonate, and the like. Alkali metal or alkaline earth metal hydrides, such as alkali metal or alkaline earth metal carbonates such as calcium carbonate, lithium hydride, sodium hydride, potassium hydride, calcium hydride, etc. Metal alkoxides such as sodium methoxide, sodium methoxide, potassium te-butoxide

(Eg, C! One C _4), Toryechiruami emissions, organic bases such like et be such as pyridine. If necessary, a catalyst such as an ammonium salt (eg, triethylbenzene ammonium chloride) may be added to the reaction system in an amount of 0.1 to 1 mol per mol of the phenol compound represented by the general formula (7). May be added. The reaction temperature is usually from 120 ° C to the boiling point of the solvent used in the reaction or a force capable of taking a range from 150 ° C to 150 ° C to the boiling point of the catalyst used in the reaction or 100 ° C. Temperatures up to C are more desirable.

The molar ratio of the starting material and the base to be used for the reaction can be arbitrarily set, but it is advantageous to carry out the reaction in an equimolar or close ratio.

After completion of the reaction, the reaction solution can be subjected to ordinary post-treatments such as extraction with an organic solvent, ozone, and the like to isolate the target compound of the present invention. If necessary, it can be further purified by usual procedures such as chromatography, distillation and recrystallization.

(Production method D)

General formula (9):

R ¹ -Z-Y -〇CH ₂ CHO

[Wherein, RZ and Y represent the same meaning as described above. ] T / JP95 / 02320

A method for producing an aldehyde compound represented by the formula (I) by reacting the aldehyde compound with carbon tetrachloride or carbon tetrabromide in the presence of a trialkylphosphine or triarylmorphine.

The above reaction can be carried out in an inert solvent in the presence of zinc metal, if necessary.

Examples of the inert solvent used include hydrocarbons such as benzene, xylene and toluene, ethers such as dimethyl ether, diisopropyl ether, tetrahydrofuran and dioxane, dichloromethane, 1,2-dichloroethane, and chloroform. And halogenated hydrocarbons such as benzene (excluding carbon tetrabromide and carbon tetrachloride).

The reaction temperature can range from 130 to the boiling point of the solvent used in the reaction or 150 ° C.

Trialkyl (e.g., 1 C _{2 D} ) phosphine or triaryl phosphine to be subjected to the reaction includes, for example, triphenylphosphine-trioctylphosphine, and metal zinc used as necessary is dust. Is preferred.

The molar ratio of the raw materials and reagents to be used for the reaction can be set arbitrarily, but 1 to 5 moles of carbon tetrabromide (tetrachloride) is used per mole of the aldehyde compound of the general formula (9). The ratio of the kill phosphine or the triaryl phosphine is 2 to 10 mol. When zinc is used, the ratio of the zinc is preferably 1 to 5 mol, or the reaction is advantageously carried out at a ratio close thereto.

After completion of the reaction, the reaction solution is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration to isolate the target compound of the present invention. If necessary, purification can be carried out by ordinary procedures such as chromatography, distillation, and recrystallization.

(Production method E) The funinol compound represented by the general formula (7) in the production method C and the general formula (10):

HO-CH ₂ CH = CX ₂

[Wherein, X represents the same meaning as described above. ]

A method for producing by reacting an alcohol compound represented by the formula: The above reaction is preferably carried out in the presence of a suitable dehydrating agent, if necessary, in an inert solvent.

Examples of the dehydrating agent used, for example, hexyl Cal positive imide dicyclohexyl, dialkyl (e.g., d-c ₄₎ § zone dicarboxylate rate Bok (Jechiruazo dicarboxylate, diisopropyl § zone dicarboxylate, etc.) Single trialkyl (Eg, C, 1 c _{2 ()} ) phosphine or triaryl phosphine (triphenyl phosphine, trioctyl phosphine, tributyl phosphine, etc.), and the like.

Examples of the solvent used include hydrocarbons such as benzene, kylene and toluene, ethers such as dimethyl ether, diisopropyl ether, tetrahydrofuran and dioxane or carbon tetrachloride, dichloromethane, chlorobenzene, and dichlorobenzene. Halogenated hydrocarbons can be mentioned.

After completion of the reaction, the reaction solution can be subjected to ordinary post-treatments such as extraction with an organic solvent, concentration, and the like to isolate the target compound of the present invention. If necessary, chromatograph The product can be further purified by filtration, distillation, recrystallization and other operations.

In (Process F) {compound of the present invention is Z = 0, 1 ^ = 0 ₃ or Q _4, and, beta = beta '(beta ¹ wherein represents an oxygen atom, a sulfur atom or NR ¹¹ , R ^u have the same meaning as above.), And Y is Yi, Y ₂ , Υ ₃ or Υ ₄ , that is, とき is Υ _{1 (} ).

—General formula (11):

ΗΒ

_{^{Wherein, Y I (), BR 2}} , R 3, R 4, i and X are as defined above _c

]

And a compound represented by the general formula (12)

AL ¹ or

[Wherein, A, RR ⁶ , L ¹ and j represent the same meaning as described above. ] The compound produced by reacting with the compound shown by these.

The above reaction is carried out in the presence of a suitable base, preferably carried out in an inert solvent _c Examples of the solvent used include ketones such as acetone, methyl ethyl ketone and cyclohexanone, 1,2-dimethoxetane, tetrahydrofuran, dioxane, dialkyl (eg, d—C ₄ ) ether (Eg, methyl ether, diisopropyl ether, etc.), polar solvents such as N.N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric acid triamide, sulfolane, acetonitrile, nitromethane, dichloromethane, Examples thereof include halogenated hydrocarbons such as chloroform, 1,2-dichloroethane, and benzene, hydrocarbons such as toluene, benzene, and xylene, and water. If necessary, a mixed solvent of these solvents can be used.

Examples of the base used include hydroxides of alkali metals or alkaline earth metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, lithium carbonate, potassium carbonate, sodium carbonate, and the like. Alkali metal or alkaline earth metal metal carbonates such as calcium carbonate, alkali metal or alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride, calcium hydride, etc. Alkyli metal alkoxides such as toxide, sodium methoxide and potassium tert-butoxide (eg, organic bases such as d-CJ, triethylamine, pyridine and the like. A catalyst such as ammonium salt (eg, triethylbenzylammonium chloride) is generally added to the system. The reaction may be carried out in an amount of 0.01 to 1 mol per 1 mol of the compound represented by the formula (11) The reaction temperature is usually from 120 ° C. to the boiling point of the solvent used in the reaction, or from 1 ° C. A force that can be in the range of 500 ° C ^ — a temperature from 5 ° C to the boiling point of the solvent used in the reaction or 100 ° C is more desirable.

The molar ratio of the starting material and the base to be used for the reaction can be set arbitrarily. 95/02320

It is advantageous to carry out the reaction at a ratio close to it.

In (Process G) (the present compound is Z = B = 0, R! = Q 3, Q 4. A Q ₇ or Q _8, and, Y is Yi, Y _2, Upsilon ₃ or Upsilon _4, that is, when Upsilon is Upsilon ₁₀₎

General formula (13):

R

ΗΟ CH- 0— Υ ₁₀ — OCH ₂ CH = CX;

[Wherein, Y ₁₀ , R ² , R ³ , R ⁴ , i and X represent the same meaning as described above. And an alcohol compound represented by the general formula (14):

Or A—C (R ⁷ ) = C (R ⁸ ) —C〇OH

A method for producing a compound represented by the formula:

The above reaction is preferably carried out in the presence of a suitable dehydrating agent, if necessary, in an inert solvent.

Examples of the dehydrating agent used, for example, hexyl Cal positive imide dicyclohexyl, dialkyl (eg, C, one c ₄₎ § zone dicarboxylate (Jechiruazoji Karubokishire Bok, diisopropyl § zone dicarboxylate Kin rate, etc.) Single thoria alkyl (Eg, C! —C ₂₀ ) phosphine or triarylphosphine (such as triphenylphosphine, trioctylphosphine, and tributylphosphine).

Examples of the solvent used include hydrocarbons such as benzene, xylene, and toluene, ethers such as getyl ether, diisopropyl ether, tetrahydrofuran, and dioxane, and carbon tetrachloride, dichloromethane, cyclobenzene, and dichlorobenzene. Halogenated hydrocarbons can be mentioned.

(Production method H) (In the compound of the present invention, Z = 〇, B = 〇, S.R ¹¹ . C (= 0) 0, a ^{_{_{R 1 = Q 3, Q 4}}} , Q 7 or Q _8, and, Y is Y physician Upsilon _2, Upsilon ₃ or Upsilon _4, i.e. Upsilon is a Upsilon _{1 ()} When)

General formula (15): R 3

L ¹ -CH-OY ₁₀ -OCH ₅ CH = C;

[Wherein, Υ ₁₀ , R ² , R ³ , R ⁴ , L ¹ and i represent the same meaning as described above. And a compound represented by the general formula (16):

Q Q 42

Q 72 Q 82

[Wherein, R ⁵ , R ⁶ , R ⁷ , R ⁸ , A, B and j represent the same meaning as described above. ] The compound produced by reacting with the compound shown by these.

The above reaction is preferably performed in an inert solvent in the presence of a suitable base. The solvent to be used include acetone, methyl E chill ketone and key Sanon cyclohexane, 1. 2-dimethyl Bok Kishetan, as tetrahydrofuran, Jiokisan, dialkyl (eg, C! One C ₄₎ ether (e.g., Ethers such as dimethyl ether, diisopropyl ether, etc.), polar solvents such as N, N-dimethylformamide, dimethylsulfoxide, hexamethylphosphoric acid triamide, sulfolane, acetonitrile, nitromethane, dichloromethane, chloroform, 1 Examples include halogenated hydrocarbons such as 1,2-dichloroethane and benzene, hydrocarbons such as toluene, benzene and xylene, and water. If necessary, a mixed solvent of these solvents can be used.

Examples of the base used include hydroxides of alkali metal or alkaline earth metal such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and calcium hydroxide, lithium carbonate, potassium carbonate, sodium carbonate, and carbonic acid. Alkali metal or alkaline earth metal hydride, such as alkali metal or alkaline earth metal carbonate such as calcium, lithium hydride, sodium hydride, potassium hydride, calcium hydride, etc. , sodium main Tokishido, sodium Muetokishido, Al force Li gold厲alkoxides such force Riumu tert- butoxide (e.g., C -! C _4), Bok Riechiruami down, and organic bases such as pyridine Ru mentioned. If necessary, a catalyst such as an ammonium salt (eg, triethylbenzylammonium chloride) may be added to the reaction system in an amount of 0.01 to 1 mol of the compound represented by the general formula (16). ~ 1 mole ratio may be added.

The reaction temperature is usually from 120 ° C to the boiling point of the solvent used in the reaction or from 150 ° C to the boiling point of the solvent used in the reaction. Temperatures up to C are desirable. / P95 / 02320

The molar ratio of the raw materials used for the reaction and base out arbitrarily set outs, etc. Moruma others it is advantageous to conduct the reaction at a ratio closer thereto _c

(Production method I) (In the compound of the present invention, 2 = 0, 6 = 〇 (= 0) ^ '1 ¹⁵

Three

And R ^1: = Q ₃ or C and 5 and Y is Y !, Υ ₂ , Υ ₃ or Υ ₄ , ie 即ち is Υ _{1 ()} )

General formula (17):

Η— CX

[Wherein, Y ₁₀ , R ² , R ³ , RR ⁵ , X and i represent the same meaning as above.

]-An amino compound represented by the general formula (18):

A—

Q 33 Q 43 [Wherein, A, R ⁵ , R ⁶ and j represent the same meaning as described above. ]

_{C) The} above reaction is preferably carried out in the presence of a suitable dehydrating agent, if necessary, in an inert solvent.

Examples of the dehydrating agent to be used include dicyclohexyl carbodiimide, dialkyl (eg, C i -C ₄ ) azodicarboxylate (eg, getyl azodicarboxylate, diisopropyl azodicarboxylate), and trialkyl. (Eg, C 1 -C _{2 ()} ) phosphine or triaryl phosphine (triphenyl phosphine, trioctyl phosphine, tributyl phosphine, etc.).

Examples of the solvent used include hydrocarbons such as benzene, kylene and toluene, ethers such as dimethyl ether, diisopropyl ether, tetrahydrofuran and dioxane or carbon tetrachloride, dichloromethane, cyclobenzene, and dichlorobenzene. And other halogenated hydrocarbons.

The reaction temperature can range from 120 ° C. to 200 ° C. or the boiling point of the solvent used in the reaction.

After completion of the reaction, the reaction solution is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration to isolate the target compound of the present invention. If necessary, it can be further purified by usual procedures such as chromatography, distillation, and repacking.

Further, among the compounds of the present invention, in the case of a compound having an asymmetric carbon atom, 95/02320

The compounds of the present invention include biologically active optically active isomers ((+)-isomer, (-) integral) and mixtures thereof in all ratios. In the case of a compound having geometric isomerism, the compound of the present invention also includes each geometric isomer having biological activity (cis isomer, trans isomer), and a mixture thereof in any ratio.

Next, specific examples of the compound of the present invention are illustrated by the following structural formulas (each substituent R ¹ represents one shown in Tables 1 to 33), but the compound of the present invention is not limited thereto. is not.

-6Z-

ZZZ0 {S6dr / IDd

€ 6051/96 OAV

OCH ₂ CH = CC ₂

320

OCH CH = C½

R] NH '

H ₃

- twenty five -

£ Z0 / S6dT / IDd

2s OCHcCH =

in

〇¾ ■

_R i ₀ ^^, OCH ₂ CH = CC ^

OCH ₉ CH = CBr ₁

320

table 1

R 'R ¹

CH ₃ CH ₃ (CH ₂ ) 6 CH (CH ₃ )

C ₃ Hs CH ₃ (CH ₂ ) 7 CH ₂

C n 3 CH 2 CH 2 CH ₃ (CH ₂ ) β CH ₂

(CH ₃ ) 2 CH CF ₃

CH ₃ (CH ₂ ) 2 CH ₂ CHF ₂

(CH ₃ ) 2 CHCH ₂ CF ₂ Br

CH ₃ CH ₂ CH (CH ₃ ) CF ₃ CH ₂

(CH ₃ ) 3 CC Fa CF ₂

C rl 3 (CH 2) a CH 2 FCH ₂ CH ₂

(CH ₃ ) 2 CHCH ₂ CH ₂ C 1 CH ₂ CH ₂

(CH ₃ ) 3 CCH ₂ B r CH ₂ CH ₂

CH ₃ (CH ₂ ) ₂ CH (CH ₃ ) I CH ₂ CH ₂

CH ₃ CH ₂ C (CH ₃ ) ₂ CHC 1 ₂ CH ₂

CH ₃ CH ₂ CH (CH ₃ ) CH ₂ CF ₂ BrCF ₂

(CH ₃ ) 2 C.HCH (CH ₃ ) CHF ₂ CF ₂

(C ₂ H ₅ ) ₂ CH CHFC 1 CF ₂

CH ₃ (CH ₂ ) CH ₂ CF ₂ BrCHF

(CH ₃ ) 2 CH (CH ₂ ) ₂ CH ₂ CC 1 ₃ CH ₂

Then i 3 (then H2) 3 then H (then Hn then tS Γ 3 then l 2

(C ₂ Hs) 2 CHCH ₂ FCH ₃ CH ₂ CH ₃

CH ₃ (CH ₂ ) 5 CH ₂ C 1 CH, CH ₂ CH ₂

CH ₃ (CH,) s CH, Br CH, CH ₂ CH ₂

CH ₃ (CH ₃ ) 5 CH (CH ₃ ) I CH ₂ CH ₂ CH ₂ Table 2

CF ₃ CH ₂ CH ₂ CHF ₂ (CF ₂ ) a CH ₂

CF ₃ CF ₂ CH ₃ CH ₂ = CH

CF ₃ CHFCF ₂ CH ₂ = CHCH ₂

CH ₃ CHC 1 CH ₂ CH ₃ CH = CHCH ₂

CH ₂ B r CHB r CH ₂ CH ₂ = CHCH ₂ CH ₂

CHF ₂ CF ₂ CH ₂ CH ₂ = CHCH (CH ₃ )

CH ₂ C 1 CH (CH ₃ ) CH ₂ = C (CH ₃ ) CH ₂

CH ₂ Br CH (CH ₃ ) CH ₃ CH ₂ CH = CHCH ₂

(CH ₂ F) CH CH ₃ CH = CHCH (CH ₃ )

(CH ₂ C 1) ₂ CH CH ₃ CH = C (CH ₃ ) CH ₂

(CH ₂ Br) ₂ CH (CH ₃ ), C = CHCH ₂

(CF ₃ ) ₂ CH CH ₂ = CHCH (C ₂ H ₅ )

FCH ₂ (CH ₂ ) CH ₂ CH ₂ = C (C ₂ H ₅ ) CH ₂

C] CH ₂ (CH ₂ ) CH ₂ CH ₂ = CHCH ₂ CH (CH ₃ )

B rCH ₂ (CH ₂ ) CH ₂ CH ₂ = CHCH (CH ₃ ) CH ₂

I CH ₂ (CH ₂ ) CH ₂ CH ₂ = C (CH,) CH ₂ CH ₂

CHo CH (CH ₂ Br) CH ₂ CH ₃ (CH ₂ ) CH = CHCH ₂

CF ₃ CHFCF ₂ CH ₂ CH ₃ CH ₂ CH = CHCH ₂ CH ₂

CH ₂ BrCH- ₂ CH (CH ₂ Br) CH ₃ CH = CH (CH ₂ ) CH ₂

(CH ₃ ) ₂ CC 1 CH ₂ CH ₂ = CH (CH ₂ ) CH ₂

FCH ₂ (CH ₂ ) CH ₂ CH ₃ CH ₂ CH = C (CH ₃ ) CH ₂

C 1 CH ₂ (CH ₂ ) CH ₂ (CH ₃ ) C = CHCH (CH ₃ )

B r CH ₂ (CH ₂ ) CH ₂ CH ₂ = CH (CH CH (CH

I CH ₂ (CH ₂ ) CH ₂ CH ₃ CH = CHCH (C ₂ H ₅ )

CH ₂ C 1 C (CH ₃ ) ₂ CH ₃ C H3 CH = C (C ₃ H ₅ ) CH ₂

CH ₂ Br C (CH ₃ ) ₃ CH ₃ CH ₂ = CHCH (CH CH ₂ CH ₃ ) Table 3

II

CF ₃ CC 1 = CHCH ₂

CH ₃ (CH ₂ ) II II 3 CH = CHCH ₂ CF ₂ B r CF = CHCH ₂

(CH ₂ = CHCH ₂ ) 2 CH CF ₃ CF = CHCH ₂

CC 1 ₂ = CHCH ₂ CH ₂

II CB r ₂ = CHCH ₂ CH ₂

CH (CH ₃ ) CC 1 2 = CH (CH ₂ ) 3 CH ₂

CH ₃ (CH 2) 4 CH = CHCH ₂ CH ₂ CH≡CCH ₂

CH ₃ (CH ₂ ) s CH = CHCH ₂ CH ₂ CH ₃ C≡CCH ₂

CH≡CCH ₂ CH ₂

LH (and H 3 Mr. H 2 Mr. H 2 CH≡CCH (CH ₃₎

CHC] = CH ₂ CH ₃ CH ₂ C≡CCH ₂

CC 1 2 = CH ₂ CH ₃ C≡CCH ₂ CH ₂

CHC 1 = CHCH ₂ CH≡C (CH ₂ ) 2 CH ₂

CHB r = CHCH ₂ CH≡CCH ₂ CH (CH ₃ )

CH ₂ = CC 1 CH ₂ CH≡CCH (CH ₃ ) CH ₂

CH≡CCH (C ₂ H ₅ )

CF ₂ = CHCH ₂ CH ₃ (CH ₂ ) 2 C≡CCH ₂

CC 1 2 = CHCH ₂ CH ₃ CH ₂ C≡CCH ₂ CH ₂

CB r ₂ = CHCH ₂ CH ₃ (CH ₂ ) 3 C CCH ₂

CHC 1 = CC 1 CH ₂ CHa (CH ₂ ) 3 C CCH 2 CH ₂

CHB r = CB r CH ₂ L π 3 \ π 2 4 nn

CH ₃ CC 1 = CHCH ₂ CH ₃ (CH ₂ ), C ≡CCH ₂ CH ₂

CH ₂ C 1 CH = CHCH ₂ CH≡C (CH ₂ ) ₃ CH ₂

CF ₃ CH = CHCH ₂ C 1 C≡CCH ₂

CH ₂ = C (CH ₂ C 1) CH ₂ B r C≡ CCH 2 Table 4

table

Five

CH ₃ (CH ₂ ) ₃ SCH, CH ₂ 2--π-Proboxycyclopentyl

(CH ₃ ) 2 CHSCH ₂ CH ₂ 2 -I-propoxycyclopentyl

CH ₃ CH ₂ SCH (CH ₃ ) CH ₂ 2-1 n-butoxy

CH ₃ CH ₂ SCH 2 CH (CH ₃ ) 2--Sobutoxycyclopentyl

CH ₃ SCH (C ₂ H ₅ ) CH ₂ 2--sec

CH ₃ SCH ₂ CH (C ₂ H ₅ ) 2--tert-butoxysic pentyl

CH ₃ CH ₂ S (CH ₂ ) CH ₂ neck hexyl

CH ₃ SCH (CH ₃ ) CH ₂ CH ₂ 2--

CH: SCH 2 CH (CH a) CH ₂ 3--Methylcyclohexyl

4--Methisolesik mouth hexylile

CH ₃ S (CH ₂ ) CH ₂ 2--Ethynolecyclohexyl

CH ₃ SCH (CH ₃ ) CH (CH ₃ ) 4--

(CH ₃ ) a CSCH ₂ CH ₂ 2.3-dimethylcyclohexyl

(CH ₃ ) ₂ CHCH ₂ SCH ₂ CH ₂ 3,4-dimethylcyclohexyl

CH ₃ CH ₂ CH (CH) SCH ₂ CH ₂ 3,5

3. 3, 5.5—Tetramethylcyclo

(CH ₃ ) 2 CHCH ₂ S (CH ₂ ) 2 CH ₂ hexylile

CH ₃ CH, CH (CH ₃ ) S (CH ₂ ) ₂ CH ₂ 3- -Methoxycyclohexylyl cyclobutyl Bill 31-Ethoxycyclohexyl cyclobutylyl 3-T-Propoxycyclohexylyl cyclopentyl 31 I Sopropoxycyclohexyl

2-Methylcyclopentyl 3-n-Butoxyhexyl

3-Methyl cylic a-pentyl 3-butyoxyl hexyl

2-Methoxymethoxy pentyl 3-sec sec-butoxysil hexyl

2-ethoxy pentyl 3-tert-butoxycyclohexyl Table 6

4--Methoxycyclohexyl J-le- (1,1,2,2-tetrafluorocyclohexyloxy) cyclopentyl

4-n—Propoxycyclohexyl 3- (3, 3, 3, 2.2, 1

4-Isopropoxycyclyl hexyl: ropoxy) cyclopentyl-1-n-butoxycyclohexyl 31- (trifluoromethyl) cyclohexyl

4-isobutoxycyclohexyl

4-sec 1-butoxycyclohexyl 4-1 (trifluoromethoxy) cyclo

4-1-tert-butoxin hexyl hexyl

3- (Trifluoromethoxy) cyclo 3- (Difluoromethoxy) cyclo

Alpha pentylille xyl

3- (difluoromethoxy) cyclo- (difuryleo-α-methoxy) cyclohexylpentyloxy j- ―Trifluoroethyl 4- (bromodifluoromethoxy) cis) Cyclopentyl hexyl-(2.2,2,1,1 —pentafluoro □ 3- (2,2.2 trifluorofluorethoxy) ethoxy Pentyl) Hexyl 1- (2-chloroethoxy) cyclo 41- (2,2,2-trifluoroethoxypentyl) cyclohex J 1-pentafluorobenzoylethyloxy) cyclohexyl 1- (2-chloro-1.1,2—trif-

Four

0 ,, 0 ，, 丄 1, 一 1 '' z z ~ 7 "ナ C Cu! 0T- Fluoroethoxy) Cyc hexyl Toxic) Cy α hexyl 1 (2-bromo-1 1, 1,2 — Trif 3- (2-chloroethoxy) cyclofluoroethoxy) cyclohexyl hexyl 320 Table 7

4- (2-methyl ethoxy) cyclo (1-methylcyclopropyl) methylhexyl (2-methylcyclopropyl) methyl

3- (2-bromoethoxy) cyclo 1-cyclobutuyl virethyl

Hexizole 2- (2-methylcycloprovir)

4-(2-bromoethoxy) cyclotyl hexyl α-butyl methysole

3— (2—black mouth 1,1, 2—triff

Cyclohexyl 2-cyclopentylethyl

4— (2—black □ —1,1,2—trif 3—pentyl propyl

(Zoleo ethoxy) Cyclohexylyl Cyclohexylometrile

3-(2-Bromo-1,1,2-trif 2-six ηHexizoleethizole

(Roloe ethoxy) Cyclohexyl 3

4— (2—Mouth mode 1, 1, 2 — Trif 2—Shik α Hexen J

(Zoleo ethoxy) Cyclohexyl 3-cyclohexene

3-(1,1,2,2 -tetrafluoro 3-methyl-2-cyclohexenyl toxoxy) cyclohexyl 3,5,5-trimethyl-1-cyclo D

4— (1,1,2,2, —Te Trafloolo Hexenizole

-Toxicyl) cyclohexyl 2-cyclopentenyl

3-(3,3,3,2,2.1 — ^ ^ Kisafluo 3-cyclobentenirile

π no π-^, ^ 10t. no) n n ヽ soil ϊ (J ヽ

4-(3,3,3,2,2, 1 — ^ 'Kisafluo (3-sic D hexenyl) methyl

□ Propoxy) Cyclohexyl 2- (3-cyclohexenyl) ethyl Cyclobutyrylmethyl (1-cyclopentenyl) methyl — 9 one

1 3-2 ^c 13-5 'Ζ

I D- jg-2 ^c ι 3- g 'ε' Ζ j a- i ^c l D-9 'Ζ a-' ά- Ζ ^c I 3-9 'ε' Ζ i- ^ J 9-2 ^c I D- 'ε' Ζ

Λ- V i o- ε ^∑ I 3--ς 'Ζ

I 3- 'd-ε ^z I,-' ε l 3- 'ά- z [D-one' Ζ

I-1 ί7 ^z t 3--1 ς '2

I- ^{e e-} i-i 9 'Ζ

1-2 13- ― ε ^ι ζ z J 9 ー 'ZI 3— ί'

z J a-ς 'ε I 3- ε

G- I 3-Z j a- ε

j a- 1

s l 3- 9 '9' 'ε' 2 d-z

^B (H) ^b H)

8 挲 Z £ Z0 / S6dT / XDd C60SI / 96 Ο / Α (Continuation of Table 8)

(Continuation of Table 8: T (O

2O C -C 1, -CH (CH ₃ ) 4--CF ₃

2 -C 1.-(CH ₂ ) 3 CH ₃ 3.5-(CF ₃ ) 2

1

2-C1, 4-CH ( CH 3) CH 2 CH copolymers 2, 4 one (CF ₃₎ ₂

2-C1, 4-CH ₂ CH (CH ₃ ) ₂ 2- -F, 4-CF ₃

2--CI, -CF ₃

2 -C 1.4 -C (CH ₃ ) 3 2.

2 -C 1, 4— (CH ₂ ) 4 CH ₃ 2--CFa. 4 -C 1

2- CI, 4-CH (CH ₃ ) (CH ₂ ) ₂ CH ₃ 2.CF ₃ , 5 -C 1

2- CI, 4-CH (CH ₃ ) CH (CH ₃ ) 2 2--B r, 4- -CF ₃

_{2 -C 1, -CH (C 2} H 5) 2 2 -. -CF 3 4 -B r

O C

2-C1, 4-C (CH ₃ ) ₂ CH ₂ CH ₃ 2--I, 4 -CF ₃

_{. 2 -B r 4 -C 2 H} 5 2 -. -F 6- C 4 one CF ₃

2 -Br, 4-(CH ₂ ) 2 CH ₃ 2.

2-Br, 4 -CH (CH ₃ ) 2 2 -CC 13 1

u

2-Br, 4- (CH ₂ ) ₃ CH ₃ 4 -CC 1 ₃

2-Br, 4-CH (CH ₃ ) CH ₂ CH ₃ 2-CHF ₂

3- CHF ₂

2 -B r; 4 C (CH ₃ ) 3 4-CHF ₂

2-Br, 4-(CH ₂ ) 4 CH ₃ 2-CF ₂ Br

2-Br, 4-CH (CH ₃ ) (CH ₂ ) ₂ CH ₃ 3-CF ₂ Br

2-Br, 4-CH (CH ₃ ) CH (CH ₃ 1

) 2 CF ₂ B r

2 -B r, 4 -CH (C 2 H 5) 2 3- CH 2 CFa

2-Br. 4-C (CH ₃ ) ₃ CH ₂ CH 4-CH ₃ CF ₃

2 -CF ₃ 3 CH ₂ CH ₃ CF ₃

3 -CF ₃ One CH ₂ CH ₂ CF ₃ (Continuation of Table 8)

3— CH ₂ C Fa C Fn 4-0CH (CH ₃ ) (CH ₂ ) ₂ CH ₃

4 -CH ₂ CF ₃ CFo 4-0CH (CH ₃ ) CH (CH ₃ ) 2

2 -OCHo 4--OCH (C ₂ H ₅ ) 2

3-OCHo 3--OC (CH ₃ ) 2 CH ₂ CHa

3-OC ₂ Hs 4--OC (CH ₃ ) 2 CH ₂ CH ₃

3 -OCH ₂ CH ₂ CH ₃ 4--0 (CH ₂ ) 5 CH ₃

3 -OCH (CH ₃ ) 2 4--〇 (CH ₂ ) 6 CH ₃

3 1 0 (CH ₂ ) 3 CHo 3.5-(C (CHa) 3) 2

3 One OCH (CH ₃ ) CH ₂ CHa 3, 5-(CH ₃ ) ₂

3 -OCH ₂ CH (CH ₃ ) 2 3--CHa .5 -CH (CHa) 2

3 1 OC (CH ₃ ) 3 3. 4 1 (CH ₃ ) 2

_{3 -0 (CH 2) 4 CH} 3 2, 4 one (CH ₃₎ ₂

3-DCH (CH ₃ ) (CH ₂ ) (CH ₂ ) 2 CH ₃ 2, 5-(CH ₃ ) ₂

3 -OCH (C ₂ H ₅ ) ₂ 2--CH (CH ₃ ) 2, 5 -CH ₃

3-0CH (CH ₃ ) CH (CH 3) 2 3- -CH ₃ , 4 -CH (CH ₃ ) 2

3-0 (CH ₂ ) 5 CH ₃ 3- -CH ₃ , 5 -CH (CH ₃ ) 2

3-0 (CH ₂ ) 6 CH ₃ 2-• C (CHa) 3, 5 CH ₃

4 -OCH3. 2--C (CH ₃ ) ₃ , 4 -CH ₃

4-0 C ₂ H ₅ 2.4-(C (CH ₃ ) ₃ ) ₂

4 -OCH 2 CH ₂ CH ₃ 2,3,5― v H 3) a

4 One OCH (CH ₃ ) 2 3, 4, 5-(CH ₃ ) 3

4 One (CH ₂ ) a CH ₃ 2, 4, 6— (CH ₃ ) 3

4 -OCH (CH ₃ ) CH ₂ CH ₃ 2, 3-(〇CH ₃ ) ₂

1〇CH ₂ CH (CH ₃ ) 2 3.5-(OCH ₃ ) 2

4 -OC (CH ₃ ) 0 2-〇CH ₃ , 4-CH ₃

4 1 0 (CH ₂ ), CHa 3.4-(OCHa) 7

(Continuation of Table 8)

/ JP95 / 02320

(Continuation of Table 8)

3-six mouth hexile 4-one phenoxy

4 —Cross mouth hexisole 21 C 1, 4C Pencil

3 —Phenyl 2-C1.4-α-hexyl

4-phenyl 21 C 1, 1 phenyl

3-cyclopentyl 21-C1.4

A — Π—Cycopene besotyl 21 C 1, 4I Pesic α-pentyl hexyl

3 — 0—cyclohexyl 21 C 1, 41

4-1-cyclohexylyl 21-C 1, -phenoxy

3-Phenoxy

9

〇

(R ¹⁴ ), (R) s

H 3 -CH (CH ₃ ) 2

2 -F 3 — C (CH ₃ ) 3

2 1 C 1 3 1 CF ₃

3 -F 3 -OCHa

3 -C 1 ϋ — Γ) Factory He

3 One Br 3 —〇 (CH ₂ ) 2 CH ₃

3-1 3 — OCH (CH ₃ ) 2

3 -C 3 100 (CH ₂ ) 3 CH ₃

3 -OCH ₂ CH (CH ₃ ) 2

-CO 2 CHa 3 -OCH (CH ₃ ) CH ₂ CH ₃ C0 ₂ C ₂ H ₅ 3 -OC (CH ₃ ) a

-C0 ₂ (CH ₃ ) 2 CH ₃ 3 -OCF ₃

One C〇 ₂ CH (CH ₃ ) 2 3 -OCHF2

-CO, C (CH ₃ ) 3 3 -OCF 2 Br

One CH ₃ 3 -OCF ₂ CHF ₂

One C ₂ H ₅ 3 —〇CH ₂ CFa

~ C n 2 CH 2 CH 3 3 -OC F2 CHFC F ₃ / 02320

(Continuation of Table 9)

3-1 SCH ₃ 3-1 (2-cyclopentenyl)

3 SC ₂ H ₅ 3 ― (3-cyclopentenyl)

3 -SCF ₂ CHF ₂ 3 1 (2-cyclopihexenyl)

3-OCH ₂ CH = CH ₂ 3 ― (3-cyclohexenyl)

3〇CH ₂ CH = CHCH ₃ 3-cycloproviroxy

3 — OCH ₂ C (CH ₃ ) = CH ₂ 3 —cyclobutyloxy

3 -OCH ₂ CH = C (CH ₃ ) 23 -cyclopentisolesoxy

3 -OCH ₂ CH = CC 12 3-cyclohexylreoxy

3 —〇CH ₂ CH = CB r ₂ 3- (2-cyclopentenyl) oxy

3 -OCH ₂ CH = CHC 1 3- (3-cyclopentenyl) oxy

3 -OCH ₂ CC 1 = CHC 1 3- (2-cyclohexenyl) acid

3 -OCH ₂ CC 1 = CH ₂ 3- (3-cyclohexenyl) oxy

3 -OCH ₂ CB r = CHB r 3-1〇C _S Hs

3- -〇CH ₂ CH = CC 1 CHo 3 (θ-CHa Cs H ₄₀ )

3-OCH ₂ CH = C (CH ₃ ) (CF ₃ ) 3-(m-CH ₃ C ₆ H, 0)

3- -〇CH ₂ C≡CH 3--(p-CH ₃ C ₆ H, 0)

3- -〇CH ₂ C = CCH ₃ 3--(oC 1 Ce H, 〇)

3- -OCH (CHo) C≡CH 3--(mC 1 C ₆ ΗΛ 0)

3--OC'H ₂ C = CC 1 3--(pC 1 C ₆ H 40)

3, OCH ₂ C≡CB r 3--(o-FCs H 0)

3--CH ₂ 〇CH ₃ 3--(m-FCe H ₄₀ )

_{_{_{3 - -CH 2 0C 2 H 5}}} 3- - (p-FCs H, 〇)

0 1 Π 2 u v u n 2) 2 U ΓΊ 3 0 0 "~ \ 0 ― Γ 3 6 6 Π 4 Reno

3- -CH _a OCH (CH ₃ ) 23--(mC F ₃ Cs H ₄ 〇)

3--Pencil Pencil 3-1 (p -C F Cs H, 0)

--Hexyl hexyl 3- (m- (CH ₃ ) 3 CC ₆ H ₄₀ )

95/02320

(Continuation of Table 9)

(1 Reno)

(Continuation of Table 9)

4-six mouth hex j reoxy 4- (p-CF 3 OC ₆ Hi 〇)

4- (2-Sik port pentenyl) old carboxymethyl 4 - CH 2 Mr. beta H ₅

4- (3-Sik port-pentenyl) Okishi 4 one 〇_CH ₂ C 6 H 5

4- (1-Sik Kisenirire to port) Okishi 4 one (o -C \ C s H, CH 2 0)

4- (2-cyclohexenyl) oxy 4- (mC 1 Cs H 4 CH ₂₀ )

4- (3-cyclohexenyl) oxy 4-(p -C 1 C ₆ H, CH ₂₀ )

4 6 Η 5 4 1 (o -FC 6 H ₄ CH ₂₀ )

_{4 -OCe H 5 4 - (mF} C 6 H 4 CH 2 0)

4-(o -C 1 Ce H 0) 4-1 (p-FC _s H, CH ₂₀ )

4 (mC 1 C ₆ H, 〇) 4-(0— B r Ce CH ₂₀ )

4- (p -C 1 C ₆ H 4 0) 4-(mB r Cs H, CH ₂ 〇)

4-1 (o -F Cs H 0) 4-1 (p -B r C s H 4 CH ₂ 〇)

4-(mF Ce H, 0) 4- (o-CH ₃ Ce H CH ₂ D)

4 (P-FCBE 0) 4- (1TI-CH3 Cs H, CH ₂ 0)

4- (o-CH ₃ Ce H, 0) 4- (p-CHa Ce H ₄ CH ₂₀ )

4-(m-CH ₃ C ₆ H 〇) 4- (0-CF3 Cs H ₄ CH ₂₀ )

4 one (p -CH ₃ Cs H, _{〇) 4- (m-CFo C 6} H <CH 2 0)

4-(oC F ₃ Cs H 40) 4- (p-CFa Ce H, CH ₂ D)

4 ― (m— CF 3 C 6 H 〇) 4-(m-CFa OCs H, CH ₂₀ )

4 one (p -CF ₃ C ₆ H, _{〇) 4- (P-CF 3 OCe} H, CH 2 0)

n

4- (m- (CHo) 3 CC ₆ H, 0) 2, 3 -F ₂

4- (P- (CH ₃ ) 3 CCB H4 D) 2, 4-F ₂

4-(m-CHo OCs H, 0) 2, 5 -F ₂

4-(p -CH ₃ 〇C ₆ H 0) 2, 6-F ₂

4-(mC F ₃ 0C _e H, 0) 3.4 -F ₂ 02320

(Table g; i%;

CT / JP95 / 02320

(Continuation of Table 9)

(Continuation of Table 9)

9 (Continuation of Table 9)

(Continuation of Table 9)

〇

_{_{3-0C 2 H 5. 4-0C (CH}} 3) 3 4 one CM. 3 -OCFa CHFCF3

3 -0C ₂ H _5. CD 4 -0CF ₃ 4— C 1. 3— 0 C 6 H 5

3-0C _a Hs, 4 -0CHF ₂ 4 1 C 1, 3 OCH 2 C ₆ Hs

〇

4-C1,3-cyclonothizolequine

3-OC2 Hs, 4-OCF2 CHF 2 4-C1, 3-cyclohexane

3-OCz Hs 4-OCFz CHFCF3 4— B r, 3 -0 CH ₃

3-OC2 Hs 4-OCF2 CF 3 4 1 Γ Β, 3 -0C ₂ Hs

3—OC ₂ H ₅ , 4— 0 C 6 H 5 4 -Β U r, 3-0 (C Η ₂ ) 2 C Η ₃

3-UL2 Hs, 4-OCH2 Cs Hs 4— Β r, 3— 0 C Η (CHa) 2 n np 11 1 r

3-OCH 2 Hs, 4-Br, 3-0 (CH 2) ₃ CH ₃

4— 〇

Link. 4-Br, 3-UCH2 CH (CHa) 2

3-DCH 2 Hs, 4-Br, 3-DCH (CH ₃ ) LHi LH ₃

4 nk hekin leoquin 4—Br, 3—0 and (CHa) 3

4— C 1, 3— 0 C ri 3 4— B r, 3— 0 C F 3

4 1 1, d _ U 2 Π S 4— B r, 3— 0 C H F 2

4-C1, 3-0 (CH ₂ ) 2 CH ₃ 4 -B r, 3-OC F 2 B r

4 C 1 3-OCH (CHa) 2 4— B r, 3 -OC F 2 C H F 2

4- CI, 3-0 (CH ₂ ) 3 CH ₃ 4— B r, 3— OC Hz CF ₃

4-C1, 3-OCH2 CH (CH ₃ ) 2 4-Br, 3-OC 2 CHi'Lr a

4-I Cl 3-OCH (CH ₃ ) CH ₂ CH ₃ 4 -Br, 3-OCs Hs

4 -C 1.3 _〇C (CHo) 3 4 -B r, 3 -OCH ₂ C _c H ₅

4 -C 1, 3 -OC F3 4-Br, 3-cyclopentyloxy

-C 1, 3-OCHF ₂ 4-Br, 3-cyclohexyloxy

4 -C 1.3 -OC F ₂ B r 4 -F. 3 -0CH ₃

4 -C 1. 3-OCF, CHF, 4— F, 3— 0C ₂ Hs (Continuation of Table 9)

(Continuation of Table 9)

(Continuation of Table 9)

2, 5-(CH ₃ ) 2, 4-0CH ₂ CF ₃ 3,5- (CHo) 2, 4-0CH ₂ C ₆ H ₅

2, 5-(CH ₃ ) 2, 4-0CF ₂ CHFCF ₃ 3, 5- (CHa) 2

2, 5-(CH ₃ ) 2, 4-0C ₆ H ₅ 4-sic a-pentyloxy

2.5-(CH ₃ ) 2, 4-OCH ₂ is H ₅ 3, 5- (CHo) 2

2, ο ·-(CH ₃ ) 2 t 4-hexylhexyloxy

4 -. Consequent opening Penchiruokishi 3 5 -C 1 _2, one 〇_CH ₃

2, 5--(CH ₃ ) 2 3.5 -C 1 2, 4 -OC 2 H ₅

4--cyclohexizoleoxy 3,5-C, 4-0 (CH ₂ ) 2 CH ₃

3, 5--(CH ₃ ) 2 -OCH 3 3,5-Cl ₂ , 4-OCH (CH ₃ ) 2

3, ο--(CH ₃ ) 2, 4-0 H ₅ 3,5- Cl ₂ , 4-0 (CH ₂ ) 3 CH ₃

3, 5--(CH ₃ ) 2, -0 (CH ₂ ) 2 CH ₃ 3,5-CU, 4-0CH ₂ CH (CHa) 2

3, 5--(CH ₃ ) 2, 4-OCH (CH ₃ ) 2 3,5-Cl ₂ , 4-OCH (CH ₃ ) CH 2 CH ₃

3, 5- ■ (CH ₃ ) 2, 4-0 (CH ₂ ) ₃ CH ₃ 3,5-Cl ₂ 4-DC (CH ₃ ) 3

3, 5- ■ (CH ₃ ) 2 3, 5— C 1 2, 4 -OC F3

4-0CH ₂ CH (CH 3) 2 3.5-C 1 2, 4-1 OCHF ₂

3, 5- (CHa) 23.5-1 C 1 ₂ , 4 -OC F ₂ B r

4-OCH (CH ₃ ) CH ₂ CH ₃ 3,5-Cl ₂ 4-OCF2 CHF ₂

3, 5- (CH,) 2, -DC (CHo) 3 3, 5-Cl ₂ , 4-OCH2 CF ₃

3, 5- (CHa) 2, 4-OCF ₃ 3, 5-CU, 4-0CF ₂ CHFCF 3

3, 5- (CHa) 2 4 -OCHF2 3. 5- C 1 2, 4 -OC 6 GH 5 Π 3) 2 4-OCF 2 Br <J> 5 - Γ1, 2 4-DCH, r fi H ¾

3, 5- (CH ₃ ) 2 4-OCF ₂ CHF 2 3, 5- Cl ₂ ,

, 5- (CH ₃ ) 2 4-0C1 CF ₃ 4-cyclohexyl pentoxy, 5- (CH ₃ ) 24-0CF ₂ CHFCF 3 3, 5- CI2,

. 5- (CHo) 2, Kishiruokishi to 4-0 H ₅ 4-Sik a Table 10

: D〇

0H Jo.

J

"»

Hu ί uo 〇HuHυ UιwE "I

u -a "l 〇Hu ^ Huol"- (Continuation of Table 10)

4-cyclohexyl 4- (p -C Ho C ₆ H, 〇) 4-(3 -pent pentenyl) 4-(o-CF ₃ C ₆ H 0) 4-(2 -pent pentenyl) 4- _{_{(m - CF 3 C 6 0}} ) 4 ( cyclohexenyl 3- consequent opening) one _{_{4 - (p -CF 3 C 6}} H, 0) 4 - ( cyclohexenyl 2- consequent opening) 4- (m- (CH ₃ ) 3 CCe H4 0) 4-cyclobutyroxy 4-(P- (CH ₃ ) 3 CCe H ₄₀ )

4-cyclobutyloxy 4- (m-CH ₃ OCs H ₄₀ )

4—Pentyloxy 4--(p -CH ₃ 0C ₆ H ₄₀ )

4- cyclohexylene carboxymethyl »Reokishi 4 one _{_{(mC F 3 OCs H 4 0}} )

4- (3-cyclopentenyl) oxy 4- (p -CF ₃ OCs H, 0)

4- (2-cyclopentenyl) oxy 4- -CH ₂ Cs Hs

4- (3-cycloπhexenyl) oxy 4- -OCH2 Ce H ₅

4- (1-cycloαhexenyl) oxy 4— (o -C 1 C ₆ H 4 CH ₂ 〇)

4- (2-cyclohexenyl) 4--(mC 1 C ₆ H, CH ₂ 〇)

4 1 C ₆ H ₅ 4-(pC 1 C ₆ H ₄ CH ₂₀ )

4 -OC ₆ HS 41 (o-FCe H ₄ CH ₂₀ )

4-(o -C 1 C ₆ H, 0) 4-(mF C ₆ H ₄ CH ₂₀ )

4 (mC 1 C ₆ H, 0) 4-(p -F Cs H 4 CH ₂₀ )

4-(p -C 1 C ₆ H 〇) 4-(o— B r C ₆ H ₄ CH ₂₀ )

4- (o-F Cs 〇) 4- (mB r C ₆ H, CH ₂₀ )

4-(m— F Cs H, 0) 4-(p -Br C ₆ H ₄ CH ₂ 〇)

4 one (P -FCB H _{<〇) 4- (0-CH3 C 6} H4 CH 2 0)

4- (θ -C Ha Ce H, 0) 4- (m-CH ₃ C ₆ W, CH ₂₀ )

4 (m— CH ₃ C ₆ H 0) 4-(P-CHO C ₆ H, CH ₂₀ )

One eight (Table 10)

4- (o-CF ₃ CBH, CH ₂ 0) 4-1 CH ₃ 3 -OCe Hs

4- (m-CF a C 6 H * CH ₂ 0) 4-CH ₃ 3-OCH ₂ C ₆ H ₅

4- (p-CFo C 6 H, CH ₂ 0) 3 -F, 4 ― OCs H ₅

4- (rn-CFo OC 6 H, CH ₂ 0) 3 -F. 4 OCH ₂ C ₆ Hs

4- (P-CF 3 OC 6 H4 CH ₂ 0) 3-C 1, 4-C ₆ Hs

2−1 F, 5 ― (PF CB H 〇) 3 — C 1, 4 -OCH ₂ C ₆ Hs

4 one F. 3 one 〇_C ₆ H ₅ 3 one _{B r, 4 -OCH 2 Ce H} 5

4 -F, 3 〇CH ₂ C ₆ H ₅ 3 1 CH ₃ 4 -OCe H ₅

4 -C 1, 3 one 〇_C _{_{_{6 H 5 3 -CH 3 4 -OC}}} H2 C 6 Hs

4 -C 1, 3 100 CH ₂ C ₆ H ₅

4 -Br, 3 CH ₂ C ₆ Hs

Table 11

CH2

(Continuation of Table 11)

4 ― CH 2 C 6 H 5 4 1 C 1, 3 1 C ₆ H ₅

4〇CH ₂ C s H ₅ 4—C 1, 3 一 0 CH ₂ C ₆ H ₅

4- (p-FCs H, 〇) 4-CH 3, 3-OC ₆ H ₅

4 (p-C) Cs 〇 4 -CH 3, 3 -0C ₆ H CH ₂ 〇

4-(p-CH u ₃ C s H, 0) 4 -B r. 3 〇 CH ₂ C ₆ H ₅

4 (m-CFa Cs H 40) 3 -F, 4-OCe H ₅

4 one (p-CF ₃ Cs H, 0) 3 -F, one 〇CH ₂ Cs H ₅

X

4-shik pliers <(R 31 C 14 -OCe Hs

4 Kishirire _{_{3 -C 1 4 -OCH 2 C 6}} H 5 to Shiku D

4-CH3, 4-CH3, 4-OCs Hs

Kishiruokishi 3-CH 3 to 4 Shikuro 4 one 〇_CH ₂ C s H ₅

4 —〇CH ₂ CH = CC 12 3—Br A 1 Hz and S Π 5

4 -OCH ₂ CH = CB r ₂ 3-C1, 4- -mouth CH 2 CH = CC1 ₂

4 — F, 3-OCs H ₅ 3-C1, 4- -DCH ₂ CH = CBr ₂

Four

JP95 / 02320 Table 1 2

(Continuation of Table 12)

(R), (R) _q

—Hiroshi Π H2 Factory _e Π R _e 5 4 ー Factory l

— Factory J TTl 2 Factory 6 i Hl 5e 4 — Γ l 3 -〇 CH ₂ C ₆ i J-54-Pr 6n Reno 4 4 ー Factory H 3, 3 -0 C ₆ Hs λ

4 -.. In-广1厂_e H [pi) 4 over厂_{_{H, 3 -0 C 6 H 4}} 2 4 one in-厂_{H Γ c Η Π) 4- R} r 5

― \ ΠΊ Γ 3 6 6 Π / 4 —〇 C ₆ H ₅

― V Ρ ― 3 6 6 Π Reno 3-F. 4 〇 CH ₂ C e H 5 i i 7 3 -C l. 4 -OC s Hs

4-cyclohexinole 3 — C l, Hs

4-sic mouth pentisoleoxy 3-CH3, -0 C ₅ Hs

4 —cyclohexyloxy 3-CH ₃ , 100 CH ₂ C 6 H 5

〇〇 O 0

4 -OCH ₂ CH = CC l ₂ 3 — B r, u Hs

4 -OCH ₂ CH = CB r ₂ 3-Cl, 4-0CH ₂ CH = CCl ₂

J (

4-F. 3 -OC ₆ Hs 3-Cl, 4-0CH ₂ CH = CBr ₂

4 One F, 3-OCH2 C e Hs

(Continuation of Table 13)

3 -0CF ₂ Br HHH

3 -OCH ₂ CF ₃ HHH

3-OCF ₂ CHF ₂ HHH

3 -〇CF ₂ CHFCF ₃ HHH

4 One F H H H

4 1 C 1 H H H

4 One Br H H H

4 -CH ₃ HHH

4 -CF ₃ HHH

4 -OCH ₃ HHH

4〇C ₂ H ₅ HHH

4 1 0 (CH ₂ ) 2 CH ₃ HHH

4 -OCH (CH ₃ ) 2 HHH

4 -OCH ₂ CF ₃ HHH -OCF ₂ CHF ₂ HHH

4 100 CF ₂ CHFCF ₃ HHH

2, 4-1 F ₂ HHH

_2.5 -F ₂ HHH

2, 6-F ₂ HHH

6, 4—r 2 2 u H H

3.5 -F ₂ HHH

3.5-(OCH ₃ ) 2 HHH

3.4-1 0CH ₂ 0 HHH (Continuation of Table 13)

3〇CH ₃ , -OCH _s Η ₅ HHH

3 F, 4- OCH (CHo) ₂ HHH

3 -C 1, 4-OCH (CH ₃ ) 2 HHH

4 -CN H H H

4 — N〇2 H H H

2,, 3-F ₂ HHH

H H H CHo

HHHC ₂ H ₅

HHH-CH ₂ CH ₂

HHH -CH (CH ₃

H CH ₃ HH

H CH (CH ₃ ) 2 HH

4 — F CH (CH ₃ ) 2 HH

4 1 C 1 CH (CH ₃ ) 2 HH

H CF ₃ HH

One F CF ₃ HH

4 One C 1 CF ₃ HH

320

table 1

(R) «, R ² R ³ R ^A (R '", R ² R ³ R ⁴

HHHH 4- 0CF ₃ HHH

4 1 F H H H 4 -CN H H H

4-1-C) H H H 4 -NO2 H H H

4 One Br HHHH CH ₃ HH

4 -CH ₃ HHHH CH (CH ₃ ) 2 HH

4 -CF ₃ HHHH CF ₃ HH

4-0CH ₃ HHHHHH CH ₃

One white one

\ 3- ε H H H

I D- 2 H H H

H c H H H

H 2 HHH b (», H) 1» H _C H

9 Takamine

g i¾

OiCrO / S6df / X3d

f 6051/96 ΟΛλ (Continuation of Table 16)

H H H 24 1 F

H H H 3 4 -F

H H H 2 4 1 Br

H H H 3 4 1 Br

HHH 2 4 1 CH ₃

HHH 3 4 -CH ₃

HHH 2 4 -CF ₃

HHH 3 4 -CF ₃

HHH 24 -OCH ₃

HHH 3 100 CH ₃

HHH 2 4 -OCF ₃

HHH 3 4-OCF ₃

H H H 2

HHH 3 4 1 C0 ₂ CH ₃

HHH 2 4 -SC 〇H ₃

HHH 3 4 1 SCH ₃

HHH 2 4 -SCF ₃

H H. H 3 4 -SCF ₃

H H H 24-N H C 0 C H 3

H H H 34 -NHCOCHo

H H H 24 -CONHCHo

H H H 3 4 -CONHCHo

H H H 2 3 1 C 1

H H H 3 3-C 1

H H H 23 -F

HHH 33 -F CT / JP95 / 02320

(Continuation of Table 16)

H H H 2 3 1 Br

H H H 3 3 1 Br

HHH 2 3 1 CH ₃

HHH 3 3 1 CH ₃

HHH 2 3 1 CF ₃

HHH 3 3 -CF ₃

HHH 2 3 -OCHa

HHH 2 3 -OCF ₃

HHH 3 3 -〇CF ₃

HHH 2 3-SCF ₃

HHH 3 3 -SCF ₃

H H H 2 3 -CONHCHo

HHH 3 3 -CONHCH ₃

H H. H 2 2 1 C 1

HHH 3 2 1 C 1

One οοτ one f one ΐ H H H 〇 n H H H 〇

I Π—— V H i H H 0

Ϊ One one f? Cl H H H 0

I

I Π— V 7 H H H 〇

I H H H 0

I one f7 o H H H 0

H H H 〇 s H H • H 0

A-y> z HHH 0

J— h n u H H H 〇 u n b V H H H 〇

H ε H H H 〇

H z H H H 0

H ΐ H H H 0

H 0 HHH 0

Z £ Z0 / S6d £ / JDd C60SI / 96 ΟΛλ 02320

(Continuation of Table 17)

〇 H H H 2 4 1 Br

0 H H H 3 4 -B r

〇 H H H 4 4 1 Br

〇 H H H 04 -CN

0 H H H 14 -CN

〇 H H H 24 -CN

〇 H H H 34 -CN

〇 H H H 44 -CN

〇 HHH 0 4 1 N〇 ₂

〇 HHH 1 4 1 N0 ₂

〇 HHH 2 4 1 N〇 ₂

0 HHH 3 4 1 N0 ₂

〇 H H H 4 4 -NO2

〇 HHH 0 4 -CO2 CH ₃

0 HHH 1 4 1 C0 ₂ CH ₃

0 HHH 2 4 -C0 ₂ CH ₃

〇 HHH 3 4 -CO2 CH ₃

〇 H. HH 4 4 -CO2 CH ₃

0 ■ HHH 04 -CH ₃

〇 HHH 14 -CH ₃

0 HHH 3 4 -CH ₃

0 HHH 4 4 1 CH ₃

0 HHH 0 4 -CF ₃

0 HHH 1 4 -CF ₃

0 HHH 2 4 -CF ₃ 95/02320

(Continuation of Table 17)

0 HHH 3 4— CF ₃

〇 H H H 4

0 HHH 0 4 100 CH ₃

〇 HHH 1 4 -0 C Η ₃

〇 HHH 2 4 -OCH ₃

〇 HHH 3 4 -0 C Η ₃

〇 HHH 4 4— 0 CH ₃

〇 H H H 0 4— 0 r. C 2 H s

0 H H H 1 4 1 2 5

0 H H H 2 4— 0 C a Hs

〇 H H H 3 4 1 U 2 H 5

〇 H H H 4.4-◦ 2 H 5

〇 HHH 0 4—U (and hl 2)

〇 HHH 2 4-0 (CH 2) 2 CH ₃

0 H H H 3 4— 0 (C H 2) 2 then H 3

0 HHH 4 4-0 (CH 2) 2 then ht ₃

〇-HHH 04 -OCH (CH ₃ )

0 HHH 14 -OCH (CH ₃ ) 2

〇 HHH 2 4 1 OCH (CH ₃ ) 2

U u Π n η 0 ΰ 4 -OCH (CH ₃ ) 2

0 HH Η 4 4 -OCH (CH ₃ )

〇 H H Η 0 4 -OCF3

〇 HH Η 1 〇 CF ₃

〇 HH Η 2 4 〇 CF ₃ 20

(Continuation of Table 17)

〇 HHH 3 4 -OCF ₃

〇 HHH 4 4 -OCF ₃

0 HHH 0 4— OCF ₂ CHF ₂

〇 HHH 1 4 -OC F2 CHF ₂

0 HHH 2 4-1 CF ₂ CHF ₂

0 HHH 3 100 CF ₂ CHF ₂

〇 HHH 4 4 -OCF ₂ CHF ₂

0 HHH 0 4 -SCH ₃

〇 HHH 1 4 -SCH ₃

〇 HHH 2 4 -SCH ₃

〇 HHH 3 4 -SCH ₃

〇 HHH 4 4 -SCH ₃

0 HHH 0 4 -SCF ₃

O C

〇 HHH 1 4 -SCF ₃

〇

0 HHH 2 4 -SCF ₃

0 HHH 3 4 -SCF ₃

0 HHH 4 4 1 SCF ₃

0 HHH 04 -CH ₃ S (〇)

〇-HHH 14 -CH ₃ S (0)

〇 HHH 2 4— CH ₃ S (〇)

0 H H H 3

■ L LJ TJ A

U Ί n Π H 4— CH ₃ S (〇)

0 HHH 0 4 1 CH ₃ S (0) 2

0 HHH 1 4 -CHo S (〇) ₂

0 HHH 24 -CH ₃ S (0) ₂ (Continuation of Table 17)

〇 HHH 3 4 -CH ₃ S (0) 2

0 HHH 4 4 1 CH ₃ s (〇) 2

〇 HHH 0 4 -1 CF ₃ s (〇)

〇 HHH 1 4 -CF ₃ s (0)

0 HHH 2 4 -CF ₃ s (〇)

0 HHH 3 4 -CF ₃ s (〇)

0 HHH 4 4 -CF ₃ s (0)

0 HHH 0 4 -CF ₃ s (〇) 2

0 HHH 1 4 -CF ₃ 5 (〇) 2

0 HHH 2 4— CF ₃ S (〇) 2

0 HHH 3 4 1 CF ₃ S (0) 2

0 HHH 4 〇 4 -CF ₃ S (0) 2

0 HHH 0 4 100 CH ₂ CH = CC 1 ₂

0 HHH 14 -OCH ₂ CH = CC 1 ₂

〇 HHH 2 4 -OCH ₂ CH = CC 1 ₂

0 HHH 3 4 -OCH ₂ CH = CC 1 ₂

〇 H, HH 4 = cc 1 ₂

〇 ■ HHH 04 -OCH ₂ CH = CB r ₂

〇 HHH 14 -OCH ₂ CH = CBr ₂

0 HHH 2 4〇 CH ₂ CH = CBr ₂

〇 H. HH 3 4 -0CH ₂ CH = CB r ₂

〇 HHH 4 4 〇 CH ₂ CH = CB r ₂

0 HHH 0 4 1 CH 2 ¹ OC H3

〇 H H H 1 4 1 CH 2 1 OCH3

〇 HHH 2 4 1 CH 2 1 OCHD / JP9S / 02320

(Continuation of Table 17)

〇 HHH 3 4 -CH ₂ OCH ₃

〇 HHH 4 4 -CH ₂ 〇CH ₃

0 HHH 0 4 -CH ₂ SCH ₃

〇 HHH 1 4 1 CH ₂ SCH ₃

〇 HHH 2 4 -CH ₂ S CH ₃

〇 HHH 3 4 -CH ₂ SCH ₃

〇 HHH 4 4 -CH ₂ SCH ₃

0 HHH 0 4 1 N (CH ₃ ) 2

〇 HHH 14 -N (CH ₃ ) 2

〇 HHH 2 4 1 N (CH ₃ ) 2

〇 HHH 3 4 1 N (CH ₃ ) ₂

〇 HHH 4 4 1 N (CH ₃ ) 2

0 H H H 04 -NHCOCH3

〇 H H H 14 -NHCOCH3

0 H H H 24 -NHCOCHo

〇 H H H 3 -NHCOCHa

〇 H H H 44 -NHCOCH3

〇 H, H H 04 -CHO

0-H H H 14 -CHO

0 H H H 24 -CHO

0 H H H 3 4 -CHO

〇 H H H 4 4 -CHO

u n Π Π U _ Π Π M ΐ 丄-1 Γ Γ-T3

0 H H H 14 -CONHCHo

0 H H H 24 -CONHCHo

〇 HHH 3 4 -CONHCHa CT / JP95 / 02320

(Continuation of Table 17)

0 H H H 4 -CONHCHo

0 HHH 0 4 -CON (CH ₃ ) 2

〇 HHH 1 4 -CON (CH ₃ ) 2

〇 HHH 2 4 -CON (CH ₃ ) 2

〇 HHH 3 4 1 CON (CH ₃ ) 2

0 HHH 4 4 -CON (CH ₃ ) ₂

0 H H H 04 4-cyclopentyloxy

0 H H H 14—cyclopentizoleodi

0 H H H 2 4—Circuit pentyloxy

0 H H H 3 4-cyclopentyloxy

0 H H H 4 4-Cyclopentyloxy

0 H H H 04 4-cyclohexizoleoxy

〇 H H H 14 -cyclohexyloxy

〇 H H H 24 4-cyclohexyloxy

〇 H H H 34-cyclohexyloxy

〇 H H H 4 —Sk α-hexyloxy

0 H. H H 0 4 -C 6 H S

〇 'H H H 1 4 1 C 6 H 5

0 H H H 2 4 1 C 6 H 5

〇 H H H 3 4 1 C 6 H 5

n Λ

1 Π n 4 1 C 6 H 5

0 HHH 0 4 1 C 6 H ₅ 〇

0 HHH 1 4 1 C 6 H ₅ 0

0 HHH 2 4 1 CBH ₅ 0

〇 HHH 3 4 -CBH ₅ 0 / JP9S / 02320

(Continuation of Table 17)

〇 H H H 4 -Cs Hs 0

〇 HHH 0 4 1 Cs H ₅ CH ₂

〇 HHH 1 4 -C ₆ Hs CH ₂

〇 HHH 2 4 1 C ₆ H ₅ CH ₂

〇 HHH 3 4 1 C ₆ Hs CH ₂

〇 HHH 4 4 -Cs Hs CH ₂

〇 HHH 0 4-1 C ₆ Hs CH ₂ 〇

〇 HHH 1 4 -C ₆ Hs CH ₂ 0

0 HHH 24 -Cs Hs CH ₂₀

0 HHH 3 4 -Cs Hs CH ₂ 0

〇 HHH 4 4 -C ₆ H ₅ CH ₂ 〇

u 1

0 HHH 04-(4-FC ₆ H ₄₀ )

u

〇 HHH 14-(4-FC ₆ H 40)

u

0 H H H 2

〇 HHH 3 4-(4 -FC ₆ H 40)

〇〇

〇

〇 H H H 4 4-(4 -FCs H, 0)

0 H H H 0 4

〇 H H H 14-(4 -C 1 Ce H 40)

〇-HHH 2 4-(4 -C 1 C ₆ H * 0)

〇 H H H 3 4-(4 -C 1 Cs H, 0)

〇 HHH 4 4-(4 -C 1 C ₆ H, 0)

U H H U 4

〇 HHH 1 4 (4 -CH ₃ Cs H, 0)

〇 HHH 2 4 (4-CHc C ₆ H, 0)

0 HHH 3 4 (4 -CH ₃ C ₆ H, 〇)

6 ΟΑλ is / 9IdXDsr / s / s-e e z

〇〇〇〇〇〇〇〇〇〇〇

G ί

υ υ u u u υ U u u υ υ

L, u u υ u m m

X 1 1 1 1 1 1 1 l 1 1 1 1 1 1 υ υ υ u U U u U υ U υ CO (TO O ro CO CO ro co ro ro

1 1 1 1 1 1 1 1 1 1 1

CO C CO CO

1 1 1 1 1 1 1 1 1 1 1

CD CO CO-CO o ro CO CO C PC X X

DC "X DC • X

X

〇〇〇〇〇〇〇〇〇〇〇〇〇〇 o 〇 o 〇〇〇〇〇〇〇 m

CT / JP95 / 02320

(Continuation of Table 17)

〇 H H H 4 3— B r

〇 H H H 0 3— CN

〇 H H H 13 1 CN

〇 H H H 23-CN

〇 H H H 3 3 1 CN

〇 H H H 4 3— CN

〇 HHH 0-1 CH ₃

1 〇 υ

0 H H H 1 -CH 〇3

〇

〇 H H H 2 -CH3

〇 H H H 3 -CH3

〇 H H H 4 -CH3

〇

HHH 0

〇 H, HH 1 3-CF ₃

〇 ■ HHH 2 3 -CF ₃

0 H H H 3

〇 HHH 4 3 -CF ₃

0 HHH 1 3-OCH ₃

〇 HHH 2 3 100 CH ₃

0 HHH 3 3 100 CH ₃

0 HHH 4 3 -0CH ₃ (Continuation of Table 17)

0 HHH 0 3 -0 C 2 Hs o HHH 1 3 one 〇_C ₂ H ₅ o HHH ₂ 3-〇_C _{_{2 Hs o HHH 3 3- 0C 2}} H 5

0 HHH 0 3 100 (CH ₂ ) ₂ CH ₃ o HHH 1 3—〇 (CH ₂ ) 2 CH ₃ o HHH 2 3 -0 (CH ₂ ) 2 CH ₃ o HHH 3 3—〇 (CH ₂ ) 2 CH ₃ o HHH 4 3—〇 (CH ₂ ) 2 CH ₃

0 HHH 0 3 -OCH (CH ₃ ) 2

〇 HHH 13 -OCH (CH ₃ ) 2

〇 H H H 2 3 -OCH (CHo) 2

0 HHH 3 3— OCH (CH ₃ ) 2

0 HHH 4 3— OCH (CH ₃ ) 2

0 HHH 0 3-OCF ₃

0 H, HH 1 3 -OCF ₃

〇. H H H 2 3-OCF3

〇 H H H 3 3 -OCF3

〇 H H H 43 -OCFa

0 H H H 0 3— S C H 3

0 HHH 1 3 -SCH ₃

〇 HHH 2 3 -3CH ₃

〇 HHH 4 3- SCH 3 (Continuation of Table 17) n H Η H n

n H Η H 1 3— S C F n H Η H 2 3— S C F n Η H 33 3— S C F a n H Η H 43-S C F

Γ) H Η H un 3 -CONHCHa o H Η H 13 -C0NHCH ₃ n H Η H 23 -CONHCH ₃ o H Η H 33 -CONHCH3 n Η Η HA 3-CONH H3

n Η Η H — Γ 0 N (C H i), n Η Η H?

3 リ C ON (CH η), n Η HH 4 3— C 0 N (CH ₃ ) ₂ o Η HH o 3 —cyclopentylyloxy o Η HH 13 -cyclopentayloxy

0 Η. H H 2 3-Cyclopentyloxy o 'Η H H 3 3-Cyclopentyloxy o Η H H 4 3-Cyclopentyloxy

0 Η H H 03 —cyclohexyloxy

H Η H H 1 3—Sheet mouth

0 Η H H 23

0 Η H H 3 3—Hexyloxy

0 Η HH 4 3 (Continuation of Table 17)

〇 H H H 0 3 — 6 H 5

〇 H H H 1 3— 6 H 5

〇 H H H 23-C 6 H 5

0 H H H 3 3-6 H 5

〇 H H H 4 3—H 6 H 5

〇 HHH 0 3— C ₆ H ₅ 〇

〇 H H H 1 3— Cs Hs 〇

0 HHH 2 3— C ₆ Hs 〇

〇 HHH 3 3 -C ₆ Hs 0

〇 H H H 4 3-Ce Hs 0

〇 H H H 0 3 ~-C 6 H 5 C H 2

〇 H H H 1 ― 6 6 H 5 C H 2

〇 H H H 20-6 H 5 C H 2

0 H H H 3 0 — then 6 H 5 C H 2

〇 H H H 4 3 ― C 6 H 5 C H 2

〇 HHH 0 3 -CB H ₅ CH ₂ 0

〇 HHH 1 3 -Cs Hs CH ₂ 〇

〇 ■ HHH 2 3-Cs Hs CH ₂ 〇

0 HHH 3 3 1 Cs Hs CH ₂ 0

〇 HHH 4 3 -C ₆ Hs CH ₂ 0

TJ TJ

u H n U 6 ― V ― Γ 6 Γΐ 4 Reno

〇 HHH 1 3-(4 -FC ₆ Η <0)

〇 H H H 2 3-(4 -F CB H, 0)

0 HHH 3 3-(4 -FC ₆ H, 0)

〇 HHH 4 3— (4-FC ₆ H, 〇)

20

(Continuation of Table 17)

〇 H H H 1 2 1 C 1

〇 H H H 2 2 1 C 1

〇 H H H 3 2 -C 1

0 H H H 4 2-C 1

〇 H H H 0 2 1 Br

〇 H H H 1 2 1 Br

〇 H H H 2 2 1 Br

0 H H H 3 2 1 Br

0 H H H 42 -B r

〇 HHH 0 2 1 CH ₃

〇 HHH 1 2 -CH ₃

0 HHH 2 2 -CH ₃

〇 H H H 3

H H 4 2-1

0 H CH ₃

u

0 HHH 0 2 -CF ₃

0 H H H 1

〇 H. HH 2

0-HHH 3 2 -CF ₃

0 H H H 4

1 丄 2 -0CH ₃

〇 HHH 3 2 -OCH3

〇 HHH 0 2 -OCF3 (Continuation of Table 17) π U u 1 LJ 1

i u n 2— 0 C F a n U U

Γ HΊ n π 2— 0 C F 1 π H l i u n

nj HH 1 H 4 2 1 OC F 3 n HHH n 2 -CONHCH3 n HHH 1 2 1 C〇NHCH ₃

0 HHH 2 2 -CONHCH3 o HHH 3 2 -CONHCH3 o HHH 42 -CONHCH ₃ o HHH 0 2 -CON (CH ₃ ) ₂ o HHH 12 -CON (CH ₃ ) 2 o H ί HH 2 2 -CON ( CH ₃ ) ₂ n H 1 HXH 1 3 2 -CON (CH ₃ ) 2 n H i H 1 H 4 2 -CON (C Ho) 2 n HH i H n 2 -Ce Hs o H 1 HH 1 2 eh 5 n H 1 HH 2 2 し eh 5 o H 1. HH 3 乙 Η Η 5 o 'HHH 4 2 ― C Η 5 o HHH o 2 -S CH ₃

〇 H H H 1 2 -SCH3

〇 HHH 2 2 -SCH ₃

H H H 3 2 -SCHo

〇 HHH 4 2 -SCH ₃

〇 HHH 0 2 -SCF ₃ (Continuation of Table 1)

〇 HHH 1 2 -SCF ₃

〇 HHH 2 2 -SCF ₃

〇 HHH 3 2 -SCF ₃

〇 HHH 4 2 -SCF ₃ s HHH 0 4-F s HHH 14 4-1 F s HHH 2 4-1 F s HHH 3 4 -F s HHH 4 4 -F s HHH 0 4-1 C 1 s HHH 1 4-1 C 1 s HHH 2 4 1 C 1 s HHH 3 4 1 C 1 s HHH 4 4— C 1 s HHH 0 4 -B rs HHH 14 4 -B rs H. HH 2 4 -B rs. HHH 3 4 −1 B rs HHH 4 4 -B rs HHH 0 4-1 CH ₃ c

Π Π u Π 丄 1 4 1 CH ₃ s HHH 2 4 1 CH ₃ s HHH 3 4 1 CH ₃ s HHH 4 4 1 CH ₃ s HHH 0 4 1 CF ₃ (Continuation of Table 17) s H Η Η 1 4 1 CF ₃

H Η Η 2 4 1 CF ₃ s Η Η Η 3 4 -CF ₃

s Η Η Η 0 4 -OCH ₃

S Η Η Η 3 4 -OCH ₃

s Η Η Η 4 4 1 OCF ₃ s Η Η Η 0 4 -S CH ₃ s Η Η Η 1 4 -S CH ₃ s Η Η Η 2 4 -S CH ₃ s,, Η Η 3 4 -S CH ₃ s' Η Η Η 4 4 -S CH ₃ s Η Η Η 0 4 -SCF ₃ s Η Η Η 1 4 -SCF ₃

S Η Η Η 2 4 -SCF ₃

S Η Η Η 3 4 -SCFo

S Η Η Η 4 4 -SCF ₃

S Η Η Η 0 4 —Cyclopentyloxy

S Η Η Η 1 4-shoulder pentyloxy (Continuation of Table 17: s HHH 24 -cyclopentyloxy s HHH 34 -cyclopenty j reoxy

S H H H 4 -cyclopentic J reoxy

S H H H 04 4-cyclohex J J reoxy

S H H H 14-Cyclohexyloxy

S H H H 24 4-cyclohexyloxy

S H H H 34—cyclohepsizoleoxy

SHHH44-cyclohexyloxy

S H H H 14 — Cs Hs

SHHH 24 -Cs Hs

s HHH 4 4 1 C ₆ H ₅

S H H H 0 -Ce Hs 0

SHHH 14 -C ₆ Hs 〇

SHHH 2 4— C ₆ Hs 〇

SH. HH 3 4— C ₆ H ₅ 〇

S 'HHH 4 4 1 C ₆ Hs 0

SHHH 0 4 -C ₆ H ₅ CH ₂

SHHH 1 4 -Cs Hs CH ₂

SHHH 2 4 -C ₆ Hs CH ₂

SHHH 3 4 -C ₆ H ₅ CH ₂

SHHH 04 -C ₆ Hs CH ₂₀

SHHH 1 4 1 Cs Hs CH ₂ 〇 (Continuation of Table 17)

SHHH 2 4 1 C ₆ H ₅ CH ₂

SHHH 4 4 -C ₆ Hs CH ₂

S H H H 03 -F

S H H H 13 -F

S H H H 2 3-F

S H H H 3 3-F

S H H H 43 -F

S H H H 0 3 1 C 1

S H H H 1 3— C 1

S H H H 2 3-C 1

S H H H 3 3— C 1

Q C

S H H H 4 3-C 1 u

S H H H 0 3 1 Br

S H H H 1 3— B r

S H H H 2 3 1 Br

S H H H 3 3 1 Br

S H, H H 4 3 1 Br

SHHH 0 3 1 CH ₃

S H H H 2

SHHH 4 3 1 CH ₃

SHHH 1 2320

(Continuation of Table 17)

s HHH 3 3-CF ₃ s HHH 4 3-CF ₃

S H H H 43 -OCHa

SHHH 0 3 -SCH ₃

SHHH 2 3 -SCH ₃

S 'HHH 4 3 -SCH ₃

SHHH 1 3 -SCF ₃

S H H H 2 3— S C F 3

S H H H 3 3 -SCFo

SHHH 4 3 -SCF ₃

S H H H 0 3 —cyclopentyloxy

HHH 13-six mouth pentyloxy (Continuation of Table 17)

S H H H 2 3 —cyclopentinoleoxy

S H H H 3 3-cyclopentizoleoxy

S H H H 4 3-cyclopentyloxy

S H H H 03 —cyclohex j reoxy

S H H H 13 Cyclohexyl

S H H H 23 -cyclohex j reoxy

S H H H 3 3-hexoxyhexoleoxy

S H H H 4 3-Cyclohexylyloxy

S H H H 0 3— C 6 H 5

S H H H 1 し —S 5

S H H H 2 3— C Β Η 5

S H H H 3 3-C ε Η 5

S H H H 4 3 ― 6 Η 5

SHHH 0 3-Cs H ₅ 〇

SH, HH 4 3-C ₆ Hs 〇

S. H H H 0 3 — s H 5 C H 2

S H H H 10 0-6 H 5 C H 2

S H H H 2 3-6 H 5 C H 2

S H H H 3 3-6 H 5 C H 2

S H H H 4 0 — then 5 H 5 C H 2

SHHH 0 3— C ₆ H ₅ CH ₂ 〇

SHHH 1 3 -C _fi H CH ₂ 〇

SHHH 2 3 -C ₆ Hs CH ₂ 〇 95/02320

(Continuation of Table 17)

S H H H 3 3 Gn 5 C H 2 〇

S H H H 4 3 ― 6 6 Π 5 C H 2 〇

NH H H H 0 H

NH H H H 1 H

NH H H H 2 H

NH H H H 3 H

NH H H H 4 H

NH H H H 04 -F

NH H H H 1 4-F

NH H H H 24 1 F

NH H H H 34 -F

NH H H H 44 -F

NH H H H 0 4— B r

NH H H H 14 -B r

NH H H H 24 -B r

NH H H H 3 4 1 Br

NH H, H H 44 -B r

NH 'HHH 0 4 1 CH ₃

NH HHH 14 -CH ₃

NH HHH 24 -CH ₃

,

NH H H H n

0 4 then Π 3

NH HHH 4 4 1 CH ₃

NH HHH 0 4 1 CF ₃

NH HHH 1 4 1 CF ₃

NH HHH 24 -CF ₃ (Continuation of Table 17)

NH HHH 3 4 1 CF ₃

NH HHH 4 4 -CF ₃

NH HHH 04 -OCH ₃

NH HHH 24 -OCHa

NH HHH 0 100 CF ₃

NH HHH 04 -S CH ₃

NH HHH 14 -S CHo

NH HHH 34 -S CH ₃

NH HHH 44 -S CH ₃

NH H, HH 04 -S CF ₃

NH. HHH 1 4 -SCF ₃

NH HHH 2 4 -SCF ₃

NH HHH 34 -S CF ₃

C "IT

N H H H H 4

NH H H H 04 -CONHCHa

NH HHH 1 -CONHCHa HHHH 24 -CONHCHa 2320

(Continuation of Table 17)

NH HHH 3 4 CONHCH ₃

NH HHH 4 4 -CONHCHa

NH HHH 14 -CON (CH ₃ ) 2

NH HHH 34 -CON (CH ₃ ) 2

NH HHH 4 4 -CON (CH ₃ ) 2

NH H H H 03 -F

NH H H H 1 3-F

NH H H H 23 -F

NH H H H 3 3 1 F

NH H H H 43 -F

NH H H H 0 3 1 C 1

NH H H H 1 3 1 C 1

NH H H H 2 3 1 C 1

NH H H H 3 3 1 C 1

NH H. H H 4 3 -C 1

NH-H H H 03-Br

NH H H H 13 -B r

NH H H H 23 1 Br

IN n Π Π u o 3 -B r

NH H H H 43 -Br

NH HHH 03 -CH ₃

NH HHH 13 -CH ₃

NH HHH 2 3 1 CH ₃ (Continuation of Table 17)

NH H H H 3

NH HHH 4 3 -CH ₃

NH HHH 0 3— CF ₃

NH HHH 13 -CF ₃

NH H H H 3 3-CF,

NH H H H 4 3-CFo

NH HHH 0 3 -CH ₃ 〇

NH HHH 1 3-CH ₃ 〇

NH HHH 2 3 -CH ₃ 〇

NH H H H 3 3-C H a 〇

NH H H H 4 3 -CHo 0

NH HHH 0 3 CO-CF ₃ 〇

NH HHH 1 3-C uF ₃ 〇

NH HHH 2 3— CF ₃ 0

NH HHH 3 3— CF ₃ 〇

NH H, HH 0 3 1 CH ₃ S

NH-HHH 1 3— CH ₃ S

NH HHH 23 -CH ₃ S

NH HHH 33 -CH ₃ S

NH HHH 43 -CH ₃ S

NH HHH 03 -CF ₃ S

NH HHH 13 -CF ₃ S

NH HHH 33 -CF ₃ S (Continuation of Table 17)

NH HHH 4 3-CF ₃ S

NH HHH 0 3 1 C〇NHCH ₃

NH H H H 13 -CONHCH3

NH H H H 2 3 -CONHCHo

NH H H H 3 3 -CONHCH3

NH HHH 4 3 -CONHCH ₃

NH HHH 0 3 1 CON (CH ₃ ) 2

NH HHH 1 3 -CON (CH ₃ ) 2

NH HHH 2 3 1 CON (CH ₃ ) 2

NH HHH 3 3— CON (CH ₃ ) ₂

NH HHH 4 3 -CON (CH ₃ ) 2

NCH ₃ HHH 13 1 CF ₃

NCH ₃ HHH 23 -CF,

NCH ₃ HHH 3 3-CF ₃

NCH ₃ HHH 4 3 -CF ₃

NCH ₃ H, HH 0 H

NCH ₃ 'HHH 1 H

NCH ₃ HHH 2 H

NCH ₃ HHH 3 H

NCH ₃ HHH 4 H

NCH ₃ HHH 04 -F

NCH ₃ HHH 1 4 1 F

NCH ₃ HHH 24 -F

(Continuation of Table 17)

NCH ₃ HHH 4 4 1 F

NCH ₃ HHH 0 4— C 1

NCH ₃ HHH 1 4 1 C 1

NCH ₃ HHH 24 -C 1

NCH ₃ HHH 3 4 1 C 1

NCH ₃ HHH 4 4 1 C 1

NCH ₃ HHH 04 -B r

NCH ₃ HHH 24 ₁ Br

NCH ₃ HHH 3 4 -B r

NCH ₃ HHH 4 4 1 Br

NCH ₃ HHH 1 4 1 CH ₃

NCH ₃ HHH 2 4 1 CH ₃

NCH ₃ HHH 4 4 -CH ₃

NCH ₃ HHH 0 4 1 CF ₃

NCH ₃ H, HH 14 -CF ₃

NCH _3. HHH 2 4 -CF ₃

NCH ₃ HHH 3 4 -CF ₃

NCH ₃ HHH 4 4 -CF ₃

n

NC H ₃ HHHU 0 Γ

NCH ₃ HHH 23-F

NCH ₃ HHH 3 3-F

One 12F One

ΓΟ ΓΟ O O CO ΓΟ CO CO CQ CO ΓΟ

CD CO 0 CO

►Satsu,,>, * G, ■ '

>-* →

* -γ- * ^ γ

(-| -i -L -A

)] =

)mouth〕"

)] = (Continuation of Table 17)

C (= 0) 0 H H H 4 4 -F

C (= D) 0 H H H 0 4— C l

C (= 0) 0 H H H 14 -C l

C (= 0) 0 H H H 2 4 1 C l

[(= 0) 0 H H H 3 4 1 C I

C (= 0) 0 H H H 4 4— C l

C (= 0) 0 H H H 0 4 1 Br

C (= 0) 0 H H H 1 4 1 Br

C (= 0) 0 H H H 2 4— B r

C (= 0) 0 H H H 3 4 1 Br

C (= 0) D H H H44 -Br

C (= 0) 0 HHH 0 4-1 CH ₃

C (= 0) 0 HHH 14 -CH ₃

C (= 0) 0 HHH 2 4 1 U CH ₃

C (= 0) 0 HHH 3 4 -CH ₃

C (= 0) 0 HHH 4 4 1 CH ₃

C (= 0) 0 H H H 0

C (= 0) 0 H, HH 14 -CF ₃

C (= D) 0 'HHH 2 4 -CF ₃

C (= 0) 0 HHH 3 4 -CF ₃

C (= 0) 0 HHH 4 4— CF ₃

C (= 0) 0 HHH 0 100 CH ₃

C (= 0) 0 HHH l 4 -OCH ₃

C (= 0) 0 HHH 2 4 -OCH ₃

C (= 0) 0 HHH 3 4 100 CH ₃

C (= 0) 0 HHH 4 4 100 CH ₃ (Continuation of Table 17)

C (= 0) 0 HHH 1 4 -OCF ₃

C (= 0) 0 H H H 4 -OCF,

C (= 0) 0 H H H 0 -CONHCH3

C (= 0) 0 HHH 1 4 1 C〇NHCH ₃

C (= 0) 0 HHH 2 4 -CONHCH ₃

C (= 0) 0 H H H 3 4 -CONHCH3

C (= 0) 0 H H H 4 4 -CONHCH3

C (= 0) QHHH 0 4 -CON (CH ₃ ) 2

C (= 0) 0 HHH 1 4 -CON (CH ₃ ) ₂

C (= 0) 0 HHH 2 4 1 CON (CH ₃ ) 2

C (= 0) 0 HHH 3 4 -CON (CH ₃ ) ₂

C (= 0) 0 HHH 4 4 -CON (CH ₃ ) 2

C (= 0) Q H H H 03 -F

C (= 0) 0 H 'H H 13 -F

C (= 0) 0-H H H 23 -F

C (= 0) 0 H H H 3 3 1 F

C (= 0) 0 H H H 43 -F

C (= 0) 0 H H H 0 3-C 1

C (= 0) 0 H H H 13 -C 1

C (= 0) 0 H H H 2 3— C 1

C (= 0) 0 H H H 3 3 1 C 1

C (= 0) 0 HHH 4 3 1 C 1 (Continuation of Table 17)

TJ T_T T_I π

C ^ = U) υ Π n Π u

η U M rl rl 1

丄 3 1 B r r / 1 n, n LJ LJ 0

New U Π Π n 3— B r r — 门, n LJ

ト u Π n Γ u Q

Ί u 3— B r

LJ LJ U A

U U U nn Π. 4 3 1 B r — LU U

r L

U n, n U nJ u 1

Π 11 丄

IJ 0

1 LU U ii Π n c 3-CH,

LJ LJ

\ -U} u Π Π n 14 0 3— CH ₃

LJ IJ

New u Γ1 l u A

n 4 3 -CH ₃ r,

Then (— = nLU n U Π i Π nu 3 -CF ₃ p / — n, n TJ TJ 1

Π n I 3-CF ₃ pr \ nn OC

L (= 0) 0 H hi rl 6 3-CF ₃

〇 (= u) u

p 门, n TJ

\ -U) U rl LJ A

ΓΊ 3-CF ₃ tJ LJ

Then U ii Π n U 3 -OCH3 r then one LJ

One r un n u 11 IJ n 1

1 3 -0CH ₃

IJ u 0

And one u n 'Π Π L 3 -OCH3

「Ichi, n 'LJ LJ LJ 0

U n Π n O 3 -OCH3

C (= 0) 0 HHH 0 3—〇CF ₃

C (= D) 0 HHH 2 3 -〇CF ₃

C (= 0) 0 HHH 3 3 1 0CF ₃

(Continuation of Table 17)

C (= 0) 0 HHH 0 3 1 C〇NHCH ₃

C (= 0) 0 H H H 13 -CONHCH3

C (= 0) 0 H H H 2 3 -CONHCHo

C (= 0) 0 HHH 3 3 -CONHCH ₃

C (= 0) 0 H H H 4 3 -CONHCH3

C (= 0) 0 HHH 0 3 -CON (CH ₃ ) 2

C (= 0) 0 HHH 1 3 1 CON (CH ₃ ) 2

C (= 0) 0 HHH 2 3 -CON (CH ₃ ) 2

C (= 0) 0 HHH 3 3 -CON (CH ₃ ) 2

C (= 0) 0 HHH 4 3 1 CON (CH ₃ ) 2

C (= 0) NH H H H 0 H

C (= 0) NH H H H 1 H

C (= 0) NH H H H 2 H

C (= 0) NH H H H 3 H

C (= 0) NH H H H 4 H

C (= 0) NH H H H 04 -F

C (= 0) NH H, H H 14 -F

C (= 0) NH. H H H 24 1 F

C (= 0) NH H H H 34 -F

C (= D) NH H H H 44 -F

u TJ LJ n

-U Nn n Π n U 1 ——Factory 1 I

C (= 0) NH H H H 1 4— C 1

C (= 0) NH H H H2 4 1 C 1

C (-0) NH H H H 3 4 1 C 1

C (= 0) NH HHH 4 4 1 C 1 tt II II II

CD C3 CD L iL iL tL 1L 'I II n tin n ii n n n π n〇 N H: H <CD CD CD C3 CD CD C3 CD C3 a C C3 "c〇 F—

D C — D — O J ^ C OO — O o

7 Θ (Continuation of Table 17)

HHH 13 1 CH ₃

C (= 0) NH HHH 23 -CH ₃

C (= 0) NH HHH 3 3 1 CH ₃

C (= 0) NH HHH 4 3-CH ₃

C (= 0) NH HHH 0 3-1 CF ₃

C (= 0) NH HHH 13 -CF ₃

C (= 0) NH HHH 23 -CF ₃

C (= 0) NH H H H 33 -CFo

C (= 0) NH HHH 43 -CF

C (= 0) NH H H H 3 3 -OCHo

C (= Q) NH H, HH 3 3 -OCF ₃

CH) NH H H H 03 -CONHCH3

C (= 0) NH H H H 13 -CONHCH3

C (= 0) NH H H H 2 3— C 0 N H C H 3

C (= 0) NH H H H 3 3 -CONHCH3

C (= 0) NH HHH 4 3 -CONHCH ₃

C (= 0) NH HHH 0 3— CON (CH ₃ ) ₂

One

One 〇

(Continuation of Table 17)

0C (= 0) HHH 2 3— CH ₃

0C (= 0) HHH 3 3 1 CH ₃

0C (= 0) H H H 43 -CHo

0C (= 0) HHH 0 3 -CF ₃

DC (= 0) HHH 13 -CF ₃

0C (= 0) HHH 2 3— CF ₃

0C (= 0) HHH 3 3 -CF ₃

0C (= 0) H H H 0 2 1 C 1

0C (= 0) H H H 1 2 1 C 1

0C (= 0) H H H 2 2 1 C 1

0C (= 0) H H H 3 2 1 C 1

0C (= 0) H H K 4 2— C 1

NHCH) H H H 0 H rat (= 0) H H H 1 H

NHC (= 0) H H H 2 H

NHC (= 0) H, H H 3 H

NHC) '' H H H 4 H

NHC (= 0) H H H 0 4 -F Rat (= 0) H H H 14 -F

LJ

NHL (N n Π ΓΊ 9 4-F

NHC (= 0) H H H 34 -F

NHC (= 0) H H H 44 -F rat (= 0) H H H 04 -C 1

NHC (= 0) HHH 1 4— C 1 3: =: 2: 3 = 3: 3:

E r: e zrz rc = c 3 = zr: e zr: HZ en rn zrz

n C D n n n n π π π π π π π n π π r ~ n π π π n

II II II II II II II II II II II It II II II II II II II II tl II II II II

CD

I re: n n: SI in a in

I

CD O CO C C C ro O ro

^

One hundred one

0 Η Η Η · (0 =) 3ΗΝ ε Η Η Η (0 =) 3ΗΝ

G g-ε ΐ Η Η Η (0 =) DHN j e- ε 0 Η Η 0 (0 =) DHN t one ε Η Η Η (0 =) 删 ι one ε ε Η Η Η (0 =) Pillow

I D- ε Η Η Η Η (0 =) 3HN ι D- ε τ Η Η Η (0 =) DHN l D- ε 0 Η Η Η (0 =) ε Η Η Η (0 = d-ε 2 Η Η Η (0 =) period d-ε ΐ Η Η Η

cdDO- P Η Η Η (0 =) 3HN c DO- s Η Η Η (0 =) DHN

^Ζ Λ30- 2 Η Η Η (0 =) 3HN

Imine) orero / s6dr / i3d

£ 60SI / 96 ΟΛλ

(Continuation of Table 17)

C (= 0) N (CH ₃ ) HHH 3 4 -CF ₃

C (= 0) N (CH ₃ ) HHH 44 -CF ₃

1 8

⁽ CH ₂ ) Factory -B--(CH, 2) i- -C wH 2,

R

(Continuation of Table 18)

〇 0 1 -OCH ₃ NH 2 1 4 1 C 1

〇 1 14 -OCH3 NH 3 14 -C 1

0 2 1 4 -OCH3 NH 0 2 4 1 C 1

〇 3 1 4 -OCH3 NH 1 2 4 — C 1

〇 0: I 4 -OCH3 day 3) 0 1 H

〇 1 I -OCH3 N (CH ₃ ) 1 1 H

0 0] L-〇OCFo rigid 3) 2 1 H

〇 1] L 4—〇CF ₃ N (CH ₃ ) 3 1 H

〇 2 1 L -OCF3 rigid 3) 0 2 H

〇 3〗 4 -OCF3 N (CH ₃ ) 1 2 H

〇 0 ∑! -OCF ₃ 3) 0 1 4 1 C 1

〇 1 ^r c N (CH ₃ ) 1 1 4--C 1

S 0 1 4 1 C 1 N (CH ₃ ) 2 1 4--C 1

S 1 1 4 1 C 1 N (CH ₃ ) 3 1 4--C 1

S 2 1 4 1 C 1 N (CH ₃ ) 0 2 4--C 1

S 3 1 4 1 C 1 N (CH ₃ ) 1 2 4--C 1

S 0 2 4 1 C 1 C (= 0) 0 0 1 H

S 1 2 4— C 1 C (= 0) 0 1 1 H

NH 0 1 H C (= 0) 0 2 1 H

NH 1 1 H C (= 0) 0 3 1 H

NH 2 1 H C (= 0) 0 0 2 H

NH 3 1 H C (= 0) 0 1 2 H

NH 0 2 H C (= 0) NH 0 1 H

NH 1 2 H C (= 0) NH 1 1 H

NH 0 1 4 1 C 1 C (= 0) NH 2 1 H

NH 1 1 4 1 C 1 C (= D) NH 3 1 H Dd X-i u υ υ u υ υ

I x κ κ re

Mouth

:: U υ u υ υ u

X a: 1 1 1 1 1 1

D:

: Mouth Mouth □

Table 19

Table 20

R ^1-

B i R ² R ³ R ⁴ j R ⁵ R ⁶ R ⁷ R ⁸ (R) q

〇 0 H H H 1 H H H H H

0 1 H H H 1 H H H H H H

0 0 H H H 2 H H H H H H

〇 1 H H H 2 H H H H H H

〇 0 H H H 1 H H H H 4-1 C 1

〇 1 H H H 1 H H H H 4— C 1 nnu H H H H 2 H H H H 4-C 1

〇 1 H H H 2 H H H H 4— C 1

〇 0 HHH 1 HHHH

〇 1 HHH 1 HHHH 4 -CF ₃

〇 0 HHH 2 HHHH 4 -CF ₃

〇 1 HHH 2 HHHH 4 -CF ₃ s 0 HHH 1 HHHHH

1 H H H 1 H H H H H H

S 0 HHH 2 HHHHH s 1 HHH 2 HHHHH s 0 HHH 1 HHHH 4-1 C 1

(Continuation of Table 2I II I 0)

0C (= 0) 1 HHH 2 HHHHH

NHC (= 0) 1 H H H 1 H H H H H

H H H 2 H H H H H H

0

NHC (= 0) L i HI t. HHH

Rat (= 0) 1 HHH 1 HHHH 4-1 CF ₃ Rat (= 0) 0 HHH 2 HHHH 4-1 CF ₃

NHC (= 0) 1 H H H 2 H H H H

Table 2 1

B i R ² R ³ IT j R ^s R ⁶ (R) «,

〇 0 H H H 1 H H H

0 1 H H H 1 H H H

〇 0 H H H 2 H H H

0 1 HHH 2 HHH

Αλ Οd / loSTs / S os n: n u j i

H

^ l-«I-l I-l ^ l Π- * Π-« ί-ί-! Π- »^-« »-

H

つ〇〇〇 [tsu n lxi l i S S ^ V ^ ^

H

A! Oϋ ε IDd

twenty three

(CH 2) ra

(R ⁹ ) R '. (CH ₂ ) _m position m

H H 10

H H 1 1

H H 2 2

H H 2 0

H H 2 1

H H 2 2

5 -F H 10

5 -F H 1

¹¹

— FH 2

One CH ₃ H 0

-OCH ₃ H 1

-OCHc H 2

6 (OC Ha) ₂ H 0

6-(〇CH ₃ ) ₂ Hi (Continuation of Table 23)

5.6-(OCH ₃ ) H

Table 2 4

(R ⁹ ) κ R '° (CH ₂ ) n, position m

U

Xi H 1 0

H H 1 1

H H 1 2

H H 2 0

H H 2 1

H, H 2 2

H 2 CH ₃ 0

H 4-1 CH ₃ 0

H 1 -CH ₃ 0

5 -OCH ₃ H 0

5 OC ₂ H ₅ H 0

5 100 (CH ₂ ) 2 CH ₃ H 0

5 OCH (CH ₃ ) 2 H 0

5 100 CF ₃ H 0 / JP95 / 02320

(Continuation of Table 24)

5 100 CHF ₂ H 0

5 -OC F ₂ B r H 0

5 100 CH ₂ CF ₃ H 0

5 -OCF ₂ CHF ₂ H ι 0

5—〇 (CH ₂ ) 2 CF ₃ H 0

6 -OCH ₃ H! 0

6 -OCH ₃ H 2 2

6—〇C ₂ Hs H 2 2

6 -OCH (CH ₃ ) ₂ H 2 1

6 -OCH (CH ₃ ) 2 H 2 2

5, 7-(CH ₃ ) 2 H 10

)

(R) _q Bonding position of naphthalene it to Z

H 1

H 2

2 1 CH ₃ 1

4 1 C 1 1

-OCH ₃ 1

1 Br 1

5 4

Naphthalene bond position with Z -OCH ₃ 2

6 One Br 2

-OCH ₃ 1

7

8

29

BB bonding position R ² R ³ R ⁴ i (R ' _q

〇 1 H H H 0 H

0 1 H H H 1 H

0 1 H H H 2 H

〇 1 H H H 3 H

〇 2 H H H 0 H

0 2 H H H 1 H Re 2 H H H 2 H u o u

UL Π 1 n ϋ H CH ₃

0 H H H 0 4— C 1

0 H H H 1 4 1 C 1

0 H H H 2 4— C 1

0 H H H 3 4 1 C 1

〇 2 HHH 0 1-B r (Continuation of Table 29)

0 2 H H H 1 1— B r

0 2 H H H 2 1 1 Br

〇 2 HHH 3 1 1 Br

〇 1 HHH 14 -OCH ₃

〇 1 H H H 24 -OCH3

〇 1 H H H 3 4 -OCH3

NH 1 H H H 0 H

NH H H H 1 H

NH H H H 2 H

NH 1 H H H 3 H

NH 2 H H H 0 H

NH 2 H H H 1 H

NH 2 H H H 2 H

NH 2 H H H 3 H

S 1 H H H 0 H

S 1 H H H 1 H

S 1 H H H 2 H

S 1 H H H 3 H

S 2 H H H 0 H

S 2 H H H 1 H

S 2 H H H 2 H

S 2 H H H 3 H

C (= 0) 0 1 H H H 0 H

C (= 0) 〇 1 H H H 1 H

C (= 0) 0 1 HHH 2 H (Continuation of Table 29)

C (= 0) 〇 1 H H H 3 H.

C (= 〇) 〇 2 H H H 0 H

C (= 0) 〇 2 H H H 1 H

C (= 0) 〇 2 H H H 2 H

C (= 〇) 〇 2 H H H 3 H

C (= 0) NH 1 H H H 0 H

C (= 0) NH 1 H H H 1 H

.C (= 0) NH 1 H H H 2 H

C (= 〇) NH 1 H H H 3 H

C (= 0) NH 2 H H H 0 H

C (= 0) NH 2 H H H 1 H

C (= 0) NH 2 H H H 2 H

C (= 0) NH 2 H H H 3 H

0C (= ◦) 1 H H H 0 H

〇c (= 〇) 1 H H H 1 H oc (= 〇) 1 H H H 2 H oc (= 〇), 1 H H H 3 H oc (= 〇) 2 H H H 0 H

OC (= 0) 2 H H H 1 H

OC (= 0) 2 H H H 2 H

OC (= 0) L Π n H H

NHC (= = 0) 1 H H H 0 H

NHC (= • 0) 1 H H H 1 H

NHC (= -0) 1 H H H 2 H

NHC (=: 〇) 1 HHH 3 H

(Continuation of Table 30)

〇 2 HH CH ₃ 1 H

〇 2 HH CH ₃ 2 H

0 2 HH CH ₃ 3 H

NH 1 HH CH ₃ 0 H

NH 1 HH CH ₃ 1 H

NH 1 HH CH ₃ 2 H

NH 1 HH CH ₃ 3 H

NH 2 HH CH ₃ 0 H

NH 2 HH CH ₃ 1 H

NH 2 HH CH ₃ 3 H

C (= 〇) 0 1 HH CH ₃ 0 H

C (= 0) 〇 1 HH CH ₃ 1 H c (= 〇) 〇 1 HH CH ₃ 2 H

C (= 0) 〇 1 HH CH ₃ 3 H

C (= 0) 0 2 HH CH ₃ 0 H c (= 〇) 〇 2 HH CH 1 H

C (= 0) 〇 2 H H CHo 2 H

C (= 0) -〇 2 HH CH ₃ 3 H

C (= 0) NH 1 HH CH 3 0 H

C (= 〇) NH 1 H H CHa 1 H

C (= 〇) NH 1 HH CH ₃ 2 H

C (= 〇) NH 1 H H CHa 3 H

C (= 〇) NH 2 HH CH ₃ 0 H

C (= 〇) NH 2 H H CHo 1 H

C (= 〇) NH 2 HH CH ₃ 2 H 95/02320

(Continuation of Table 30)

C (= 〇) NH 2 H H CH H Table 31

(Continuation of Table 31)

95/02320 Table 32

R] =

R ² R ³ R ⁴ 1 (R ¹⁴ ), complex position

3 H H H 0 H

3 H H H 06-C1

3 H H H 06-Br

3 H H H 0 6-1

3 HHH 06-CH ₃

Q n

0 Π u H H fi-CFr,

₃ HH CH 3 0 H

3, H H H 1 H

3 H H H 2 H

3 H H H 3 H

3 H H H 4 H

3 H H H 5 H

3 H H H 6 H

3 HHH 1 5-CH ₃

3 HHH 2 5-CH ₃

3 HHH 3 5-CH ₃ (Continuation of Table 32)

3 HHH 4 5-CH ₃

3 HHH 5 5-CH ₃

3 HHH 6 D-CH ₃

3 HH CH ₃ 1 6-CH 3

3 HH CH ₃ 2 '6-CH 3

3 HH CH ₃ 3 6-CH 3

3 H H H 4 6-CH 3

3 H H H 56-CH 3

3 H H H 6 6-CH 3

3 H H H 16-CI

3 H H H 26-Cl

3 H H H 3 6- CI

3 H H H 46-Cl

3 H H H 56-Cl

3 H H H 6 6-Cl

3 H H H 16-Br

3 H H H 26-Br

3 H H H 36-Br

3 H H H 46-Br

3 H H H 56-Br

3 H H H 66-Br

3 H H H 1 6-1

3 H H H 2 6-1

3 H H H 3 6-1

3 H H H 4 6-1

3 HHH 5 6-1 (Continuation of Table 32)

3 H H H 6 6-1

3 HHH 16-CF ₃

3 HHH 26-CF ₃

3 HHH 36-CF ₃

3 HHH 4 6-CF ₃

3 HHH 56-CF ₃

3 H H H 6 6-CF 3

3 H H H 1 2-C1

3 H H H 2 2-CI

3 H H H 3 2-CI

3 H H H 4 2-C1

3 H H H 5 2-CI o t cn

π

3 H H H 2

3 H H H 3 2, 6-C U

3 H H H 4

3 HHH 5 2, 6-Cl ₂

3 HHH 6 (Continuation of Table 32)

3 H H H 1 5, 6-C

3 H H H 2 5.6-C l 2

3 H H H 3

2 H H H 26-Cl

2 H H H 36-Cl

2 H H H 46-Cl

2 'H H H 56-Cl

2 H H H 66-Cl

2 HHH 0 5-CF ₃

1

2 H Π ΓΊ 丄 5-CFo

2 HHH 2 5-CF ₃

2 HHH 3 5-CF ₃

2 HHH 4 5-CF ₃ (Continuation of Table 32)

2 HHH 5 5-CF ₃

2 H H H 0 5-C 1

2 HHH 6 5-CF ₃

2 H H. H 15-C I

2 H H H 2 5-C 1

2 H H H 3 5-C1

2 H H H 4 5-C1

2 H H H 5 5-C1

2 H H H 6 5-C1

2 H H H 0 3-D

2 H H H 1 3-CI

2 H H H 2 3-CI

2 H H H 3 3- CI

2 H H H 4 3-CI

2 H H H 5 3-CI

2 H H H 63-CI

2, H H H 0 5-Br

2 H H H 1 5-Br

2 H H H 2 5-Br

2 H H H 3 5-Br

2 H H H 4 5-Br

2 H H H 5 5-Br

2 H H H 6 5-Br

2 H H H 0 3, 5- (CF 3)

2 HHH 1 3, 5-(CF 3) One ZLl-

H ε Η Η Η

H Η Η Η

H ϊ Η Η Η

H 0 Η Η Η

1]-9 'N'3-ζ 0 Η Η Η ΗεΗ3Γ ^E d -9' 5 Έ 0 Η Η Ζ Ζ cd -9 'C' C 0 Η Η Η 1 cd3-5 '1]-ε 9 Η Η Η 'Ζ

^C d3-C 'ID-e Η Η Η' Ζ

f Η Η Η Ζ cd3-5 Ί3-ε G Η Η Ζ Ζ cd3-5 Ί3-8 2 Η Η Η Ζ

^E d3-S Ί3-Ε ΐ Η Η Η Ζ cd3-5 Ί3-ε 0 Η Η Η Ζ

^Z I3-S 'ε 9 Η Η Η Ζ

^Σ ΐ3-ς 'e 5 Η Η Η Ζ

Η Η Η Ζ

ε Η Η Η Ζ

² 13-5 Έ Η Η Η Ζ

ΐ Η Η Η Ζ

² ns' ε 0 Η Η

² ( ^ε d3) -s ^ι ε 9 Η Η Η Ζ

² ( ^cd d)-s' ε g Η Η Η Ζ ζ ( ^cd d3) -5 Έ Η Η Η Ζ

² ( ^ε dD) -5 Έ ε Η Η Η ε ε ( ^c d3) -5 'C ζ Η Η Η Ζ

∑CrO / S6df / 13d

€ 60Sl / 96O / A (Continuation of Table 32)

4 H H H 4 H

4 H H H 5 H

4 H H H 6 H

4 H H H 0 2, 3, 5, 6-F,

4 HH CH ₃ 0 H

4 HH CH ₃ 1 H

4 HH CH ₃ 2 H

4 HH CH ₃ 3 H

4 HH CH ₃ 4 H

4 HH CH ₃ 5 H

4 HH CH ₃ 6 H

2 HH CH ₃ 0 H

2 HH CH ₃ 1 H

τ τ τ τ

2 HH CH ₃ 2 H

2 HH CH ₃ 3 H

2 HH CH ₃ 4 H

2 HH CH ₃ 5 H

2 HH CH ₃ 6 H

Table 33

Complex degenerate BR ² R ³ R 1 (R), binding position

2 〇 H H H 0 H

2 〇 H H H 1 H

2 0 H H H 2 H

2 〇 H H H 3 H

2 0 H H H 4 H

2 〇 H H H 5 H

2 0 H H H 6 H

2 H H H H 0 H

2-NH H H H 1 H

2 NH H H H 2 H

2 NH H H H 3 H

2 NH H H H 4 H

2 S H H H 0 H

2 S H H H 1 H

2 S H H H 2 H

2 SHHH 3 H (Continuation of Table 33)

2 NH H H H 5 H

2 NH H H H 6 H

2 S H H H 4 H

2 S H H H 5 H

2 S H H H 6 H

2 0 H H H 0 5-C1

2 0 H H H 1 5-C1

2 〇 H H H 2 5-C1

2 〇 H H H 3 5- CI

2 0 H H H 4 5-C1

2 〇 H H H 5 5-C1

20HHH65-CI

2 NH H H H 0 5-C1

2 NH H H H 1 5-C1

2 NH H H H 2 5-C1

2 NH H H H 3 5- CI

2 NH H H H 4 5-C1

2 NH H H H 5 5-C1

2 NH H H H 6 5-C1

2 S H H H 0 5-C1

2 S H H H 1 5-C1

2 S H H H 2 5-C1

2 S H H H 3 5-C1

2 s H H H 4 5-C1

2 s H H H5 5-C1

2 s HHH 65-CI (Continuation of Table 33)

2 N-CHa H H H 0 5-C1

2 N-CH ₃ HHH 1 5-C1

2 N-CH ₃ HHH 2 5-C1

2 N-CH ₃ HHH 3 H

2 N-CH ₃ HHH 4 H

2 N-CH ₃ HHH 5 H

2 N-CH ₃ HHH 6 H

2 NH HHH 0 5-CH ₃

2 NH HHH 3 5-CH ₃

2 NH HHH 4 5-CH ₃

2 〇 HHH 1 5-CH3

2 〇 H H H 4 5-CH3

2 〇 H H H D 5-CH3

? 0 HHH 6 5-CH ₃

2 s HHH 0 5-CH ₃

(Continuation of Table 33)

2 c LJ C

Π Γ1 rl J i] -shi H3 η LJ

ί o c Π M n 0 C ς pu

-

ί) one η η TJ

NH n n n LJ 1

1 ϋ of η LJ

L Iin i 11 l ά 9 0 01 Otsu N wun L rJl T nJ Π 0

0 ϋ ΟΓ ο t fLiIU

6 n rl fl n A J ul

0 Τ_Γ T

L [n J

Π 1 1 J J 01 ο

Otsu NH ii n tj

Π D ϋ R DrI n C_ i U inn _r

u ϋ D ϋΓ rr

u x 1

11 rl 丄

UL rJl n nr CQ 0 D1

ϋ R orr

0 n u n 1 n U A ϋ 5— D RIr

9 L n n u n u n J 5— Rr

O 6 n u n u n u n 0

o c TJ TJ T ΠJ n u Rr

D DI

2 s H H H 35-Br

2 s H H H 4 5-Br

2 s H H H55-Br

2 s HHH 6 5-Br

20

(Continuation of Table 33)

2 〇 HHH 0 3-Cl, 5-CF ₃

2 〇 HHH 1 3-Cl, 5-CF ₃

2 0 HHH 2 3-Cl, 5-CF ₃

2 〇 H H H 4 3-Cl, 5-CF 3

2 〇 HHH 5 3-Cl, 5-CF ₃

2 SHHH 0 3-Cl, 5-CF ₃

2 SHHH 3 3-Cl, 5-CF ₃

2 's HHH 4 3-Cl, 5-CF ₃

2 s HHH 5 3-Cl, 5-CF ₃

2 s HHH 6 3-Cl, 5-CF ₃

0

6 n n u Π n u 5— Nil-

2 〇 HHH 1 5-N0 ₂

2 〇 H H H 3 5-NO 2

2 〇 HHH 4 5-N0 ₂ / JP95 / 02320

(Continuation of Table 33)

2 0 HHH δ 5-ND ₂

2 0 HHH 6 5-N0 ₂

2 〇 _{HHH 0 3-N0 2, 5-} Br

2 〇 _{HHH 1 3-N0 2, 5} -Br

2 〇 HHH 2 3-NQ ₂ , 5-Br

2 〇 _{HHH 3 3-N0 2, 5} -Br

2 〇 _{HHH 4 3-N0 2, 5} -Br

2 〇 _{HHH 5 3-N0 2, 5} -Br

2 〇 _{HHH 6 3-N0 2, 5} -Br

2 〇 _{HHH 0 3-N0 2, 4} -CH 3

2 〇 _{HHH 1 3-N0 2, 4} -CH3

2 〇 HHH 2 3-ND ₂ , 4-CH ₃

2 〇 _{HHH 3 3-N0 2, 4} -CHo

2 〇 _{HHH 4 3-N0 2, 4} -CH 3

2 〇 HHH 0 4-CHo, 5- N0 2

2 〇 HHH 1 4-CH3, 5- N0 2

2 '〇 HHH 2 4-CH ₃ , 5-NO2

2 〇 _{HHH 3 4-CH 3, 5} -N0 2

2 〇 HHH 4 4-CH3, 5-N. _Two

2 〇 HHH 5 4-CHa, 5-NQ ₂ L 0 π nu Π 1 u1 u 4 shi 113, j 11U2

3 〇 H H H 0 H

3 〇 H H H 1 H

3 〇 HHH 2 H 02320

(Continuation of Table 33)

3 〇 H H H 3 H

3 0 H H H 4 H

3 0 H H H 5 H

3 〇 H H H 6 H

3 〇 HHH 06-CH ₃

3 〇 HHH 16-CH ₃

3 0 HHH 26-CH ₃

3 〇 HHH 3 6-CH ₃

3 〇 HHH 4 6-CH ₃

3 0 HHH 56-CH ₃

3 〇 HHH 6 6-CH ₃

3 〇 H H H 0 5-C1

3 0 H H H 1 5-Cl

3 0 H H H 2 5-C1

3 〇 H H H 3 5- CI

3 〇 H H H 4 5- CI

3 〇 H H H 5 5-Cl

3 〇 H H H 6 5-Cl

3 0 H H H 0 2-C1

3 0 H H H 1 2-C1

30HHH22-CI

3 〇 H H H 3 2-C1

3 〇 H H H 4 2-C1

3 〇 H H H 0 2-C1

3 〇 HHH 6 2-C1 (Continuation of Table 33)

3 〇 HHH 0 2-I, 6-CH ₃

3 〇 HHH 1 2-1, 6-CH ₃

3 〇 HHH 2 2-I, 6-CH ₃

3 〇 HHH 3 2-L 6-CH3

3 0 HHH 5 2-1, 6-CH ₃

3 0 H H H 6

3 NH H H H 0 H

3 NH H H H 1 H

3 NH H H H 2 H

3 NH H H H 3 H

3 NH H H H 4 H

3 NH H H H 5 H

3 NH-H H H 6 H

4 S H H H 0 H

4 S H H H 1 H

4 s H H H 2 H

4 s H H H 3 H

4 s H H H 4 H

4 s H H H 5 H

4 s HHH 6 H

nnu H

4 NH H H H 1 H

4 NH H H H 2 H

4 NH HHH 3 H (Continuation of Table 33)

4 NH H H H 4 H

4 NH H H H 5 H

4 NH H H H 6 H

4 0 H H H 0 H

4 〇 H H H 1 H

4 0 H H H 2 H

4 〇 H H H 3 H

4 〇 H H H 4 H

4 〇 H H H 5 H

4 〇 H H H 6 H

4 S H H H 0 ύ, ΰ, 5, D-Cl

4 SHHH 1 2, 3, 5, 6-CK

4 SHHH 3 2, 3, 5, 6-CI 4

4 S H H H 6 2, ΰ, 5, 6-CI 4

2 0 HHH 0 5-CF ₃

2 〇 HHH 1 5-CF ₃

2 〇 H H H 2 5-CF 3

0

L H H H 3 5-CF 3

2 〇 HHH 4 5-CF ₃

2 〇 HHH 5 5-CF ₃

2 〇 HHH 6 5-CF ₃

2 SHHH 0 5-CF 3 (Continuation of Table 33)

2 SHHH 1 5-CF ₃

2 SHHH 2 5-CF ₃

2 NH HHH 1 5-CF ₃

2 NH HHH 2 5-CFa

2 NH HHH 5 5-CF ₃

2 N (CH ₃ ) HHH 0 5-CF ₃

2 N (CH ₃ ) HHH 1 5-CF ₃

2 C (= 0) 0 H H H 0 H

2 C (= 0) 0 H H H 1 H

0 n u

(U H Π Π 6

2 C (= 0) 0 H H H 3 H

2 C (= 0) 0 H H H 4 H

2 C (= 0) 0 HHH 5 H oo

o

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(Continuation of Table 33)

(Continuation of Table 33)

2 NHC (= Q) HHH 6 3-C1, 5-CF ₃

2 0 HHH 1 3-Br, 5-CF ₃

2 〇 HHH 2 3-Br, 5-CF ₃

2 〇 H H H 3 3-Br, 5-CF3

2 〇 HHH 4 3-Br, 5-CF ₃

2 〇 H H H 6 3-Br, 5-CF3

2 s HHH 4 3-Br, 5-CF ₃

2 NH HHH 0 3-Br, 5-CF ₃

2 N (CH ₃ ) HHH 0 3-Br, 5-CFo

2 N (CH ₃ ) HHH 1 3-Br, 5-CF ₃

2 Go 3) HHH 2 3-Br, 5-CFo

(Continuation of Table 33)

2 NHC (= 0) HHH 0 3-Br. 5-CF ₃

2 NHC (= 0) HHH 1 3-Br, 5-CF ₃

2 NHC (= 0) H H H 2

2 NHC (= 0) HHH 3 3-Br, 5-CF ₃

2 NHC (= 0) H H H 4 3-Br, 5-CF3

2 NHC (= 0) H H H 5 3-Br, 5-CF3

2 NHC (= D) H H H 6 3-Br, -CF3

2 〇 HHH 0 3, 5- (CF ₃ ) 2

2 〇 HHH 1 3, 5- (CF ₃ ) 2

2 〇 HHH 2 3, 5- (CF ₃ ) 2

2 0 HHH 3 3, 5- (CF ₃ ) 2

2 〇 HHH 4 3, 5- (CF ₃ ) 2

2 〇 HHH 5 3, 5- (CF ₃ ) 2

1

2 〇 HHH 63, 5- (CF ₃ ) 2

3, 5- (CF 1

2 SHHH 0 ₃ ) ₂

2 SHHH 1 3, 5- (CF ₃ ) 2

2 SHHH 2 3, 5- (CF ₃ ) ₂

2 s HHH 3 3, 5- (CF ₃ ) 2

2 s HHH 4 3, 5- (CF ₃ ) 2

2 s HHH 5 3, 5- (CF ₃ ) 2

2 s HHH 6 3, 5- (CF ₃ ) 2

2 NH HHH 0 3, 5- (CF ₃ ) ₂

2 NH HHH 1 3, 5- (CF ₃ ) 2

2 NH HHH 2 3, 5- (CF ₃ ) 2

2 NH HHH 3 3, 5- (CF ₃ ) 2

2 NH HHH 4 3.5- (CF ₃ ) ₃ (Continuation of Table 33)

2 NH HHH 53, 5- (CF ₃ ) ₂

2 NH HHH 6 3, 5- (CF ₃ ) 2

2 Go 3) HHH 0 3, 5- (CF ₃ ) ₂

2 Go 3) HHH 1 3, 5- (CF ₃ ) ₂

2 N (CH ₃ ) HHH 23,5- (CF ₃ ) ₂

2 N (CH ₃ ) HHH 3 3, 5- (CF ₃ ) ₂

2 N (CH ₃ ) HHH 4 3, 5- (CF ₃ ) ₂

2 Go 3) HHH 5 3, 5- (CF ₃ ) ₂

2 N (CH ₃ ) HHH 63,5- (CF ₃ ) ₂

2 C (= 0) 0 HHH 0 3, 5- (CF ₃ ) 2

2 C (= 0) DHHH 1 3, 5- (CF ₃ ) ₂

2 C (= 0) 0 HHH 2 3, 5- (CF ₃ ) ₂

2 C (= 0) 0 HHH 3 3, 5- (CF ₃ )

2 C (= 0) 0 HHH 4 3, 5- (CF ₃ ) ₂

2 C (= 0) 0 HHH 53, 5- (CF ₃ ) ₂

2 C (= 0) 0 HHH 6 3, 5-(CF ₃ ) ₂

2 C (fD) NH HHH 0 3, 5- (CF ₃ ) 2

2 C (= D) NH H H H 1 3, 5-(CFa)

2 C (= 0) NH HHH 2 3, 5- (CF ₃ ) 2

2 C (= 0) NH HHH 3 3, 5- (CF ₃ ) 2

2 C (= 0) NH HHH 3, 5-(CFa) ₂

2 C (= 0) NH HHH 5 3.5- (CF ₃ ) 2

2 C (= 0) NH HHH 63,5- (CFa) ₂

2 C (= 0) N (CH ₃ ) HHH 0 3, 5- (CF ₃ ) 2

2 C (= 0) N (CH ₃ ) HHH 1 3, 5- (CF ₃ ) 2 (Continuation of Table 33)

2 C (= 0) N (CH ₃ ) HHH 23,5- (CF ₃ ) 2

2 C (= 0) N (CH ₃ ) HHH 3 3,5- (CF ₃ ) 2

2 C (= 0) N (CH ₃ ) HHH 4 3.5- (CF ₃ ) 2

2 C (= 0) N (CH ₃ ) HHH 53,5- (CF ₃ ) 2

2 C (= 0) N (CH ₃ ) HHH 63,5- (CF ₃ ) 2

2 NHC (= 0) HHH 0 3, 5- (CF ₃ ) 2

2 Rat (= 0) HHH 1 3, 5- (CF ₃ ) 2

2 NHC (-O) HHH 2 3.5- (CF ₃ ) 2

2 Vertical (= 0) HHH 3 3, 5- (CF ₃ ) 2

2 NHC (= 0) HHH 4 3, 5-(CF ₃ ) 2

2 NHC (= 0) HHH 5 3, 5- (CF ₃ ) 2

2 Vertical (= 0) HHH 6 3, 5- (CF ₃ ) 2

3 S H H H 0 H

3 S H H H 1 H

3 S H H H 2 H

3 s H H H 3 H

3 s H H H 4 H

3 s H H H 5 H

3 s H H H 6 H

3 C (= 0) 0 H H H 0 H

3 C (= 0) 0 H H H 1 H

3 C (= Q) 0 H H H 2 H

3 C (= 0) 0 H H H 3 H

3 C (= 0) 0 H H H 4 H

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nn (―) r-} on 'IITTTT | ^J i \

3 ^^ Θ

M O69i, c

Od J

C O CO

X X

X a m

o n

rrr t_J C_) CJ z: 3 = a =

CD CD CD CD CD

II II II II II II

m C_J J (U C_) CJ C-J

Q

CO CO CO CO CO O CO

Next, a method for producing an intermediate compound when producing the compound of the present invention will be described.

The compound represented by the general formula (4) can be produced, for example, according to the following reaction formula (I).

Reaction formula (I)

HO-Y ₁₀ -OH ^C ^ ¹ - ^CX?, HO- Y ₁₀ -OCH ₂ CH = C ₂

[Wherein each symbol has the same meaning as described above. ]

Compound represented by the general formula (2), i.e., among the compounds Ru represented by the general formula (6), !, Y is Upsilon Upsilon _2, Upsilon ₃ or Upsilon _4, i.e. Upsilon is Y _lt) compound The product can be produced, for example, according to the reaction formula (II).

/ JP95 / 02320

Reaction formula (π)

HO-Y]. -OH * "" ^¾ ~ ► ΗΟ-Ύ ₁₀ — OD ¹ (I)

NH, -Y _I0 -OH amino group << .tfNH— Y ₁₀ -OH

(ΙΠ)

Η ₂ Ν-Ύ ₁₀ -ΟΡ '1) Diazotization

HS-Y _{] 0} -OD (IV)

(II) 2) EtOCS-SK

3) H ₃ 0 ⁺

H-ZY ₁₀ -OD ¹ D ³ -Z -Y _J0 -OD

CCD, αι), (in) or (iv))

L ^, -CH, CH = CX

D ^d -ZY ₁₀ -OH D ³ -ZY J _in OO ^ C ^ H, 2C, H = CX, deprotection

H- Z -Y ₁₀ -OCH, CH = CX, m

[Wherein DD ² and D ³ represent protecting groups that can be selectively removed from each other. For example, D ¹ Habe Njiru group, D ² is Asechiru group, D ³ in the case of Z is 0 or S Benzoiru group, Z is a case of NR ¹⁶ tert-butyl O alkoxycarbonyl group (B oc group). R ¹⁶ represents an alkyl group having 1 to 3 carbon atoms. Other symbols have the same meanings as above. ]

The compound represented by the general formula (7) is, for example, a compound represented by the reaction formula (Π) or It can be prepared according to (IV) ₍

Reaction formula (H)

L ¹ ^^

H- ZY-OD ^J R ¹ -Z- Y-OD ¹

base

Wherein the symbols have the same meanings as described above. However, this does not apply when R ¹ represents. ]

Reaction formula (IV)

Bases (eg, NaOH, NaH, K ₂ C (¾)

- 1 _"- ₇ - ν copper or copper Ha ⁰ Gen product (for example

Q “L +-Z— ₀ — 0D if CuC ^) '

Q -ZY ₁₀ -ΟΏ ¹ Deprotection, Qi-Z-Yjo-OH

[Wherein each symbol has the same meaning as described above. ]

The compound represented by the general formula (9) can be produced, for example, according to the reaction formula (V).

Reaction formula (V) RI_ _Z _Y_ _OH L ^J -C¾CH (OC _? H _B ).

^{_{R 1 - 2- Y - OCH 2}} CH (OC 2 H 5) 2 H 3 0 +

(Eg, S-acetic acid)

R ¹ -Z-Y-OCH ₂ CHO

[Wherein each symbol has the same meaning as described above. ]

Among the compounds represented by the general formula (7), the compound wherein Y is Y ₅ , Υ ₆ , Υ Υ, Υ ₉ can be produced, for example, according to the reaction formula (VI).

Reaction formula (VI)

ΗΟ-Υ _ιΓ 0— D ^l I)

1) Tosylation 1) Tosylation

,. 2) R ^I6 NH 2) EtOGSSK

R ¹⁶ NH— Yu-OD ¹ !!) 3) Ethylenediamine, monole

Organic bases such as holin

HS-Factory 0-D ¹ m)

HZ-Yn-0-D ¹ ^{K Lj} R Ζ— Y _u —0— D ¹

Base

(IX Π) or] H))

Deprotection

ー Z— Y _u — OH Wherein represents _{_{_{Υ 5, Υ 6, Υ 7}}} , Υ 8 or Upsilon _9, the other symbols have the same meanings as above follow. ]

The compound represented by the above general formula (8) and the alcohol compound represented by the general formula (10), which are intermediates for the production of the compound of the present invention, are commercially available or may be used according to the reaction formula (νπ). Can be manufactured. Reaction formula (νπ)

N-chlorosuccinimide, N-bromosuccinimide, or bromine ^

X = CHCH.

Radially open β¾

—

Messil mouth lid or Tossil mouth lid

X ₂ C = CCH ₂ OH

Base

[Wherein, L ² represents a base atom or a bromine atom, L ³ represents a mesyloxy group or a tosyloxy group, and X has the same meaning as described above. ]

Among the compounds represented by the above general formulas (3) and (5), which are intermediates for producing the compound of the present invention, R ¹ is R (where R represents Q ₂ or Q ₃ among R ¹ ). The compound (1) is commercially available or can be produced, for example, by the method of the following reaction formulas (W) and (K). The aldehyde compound represented by the general formula A—CHO (where A represents the same meaning as described above), which can be a starting compound for producing the compound represented by the general formula (5), is, for example, It can be obtained by the method described in the following document.

Francocarbonaldehyde

Zh. Org. Khini., 11, 1955;

Tetrahedron., 39 3881;

Chem. Pharm. Bull., 28, 2846 etc.

Thiofanboaraldehyde

Tetrahedron., 32, 1403

Zh. Obshch. Khim., 34. 4010;

Bull. Soc. Chim. France., 479 (1963) etc.

Pyrrole carbaldehyde

Beilstein., 21, 1279 etc.

Isothiazole carboxaldehyde

J. Medicin. Chem., 13, 1208;

J. Chem. So. 46 (1964) etc.

Virazol carboaldehyde

Chem. Ber., 97, 3407;

J. Chen. Soc., 3314 (1957), etc.

Imidazole carboaldehyde

J. Pharm. Soc.. Japan., 60, 184;

J. Amer. Chem. Soc., 71, 2444 etc.

Thiazolecarbaldehyde 95/02320

JP-A-59-206370;

Chem. Ab., 62, 7764d;

Chem, Ber., 101, 3872;

JP-A-59-206370 etc.

Thiadeazole carbaldehyde

U.S. Patent No. 1113705, etc.

Reaction formula (W)

(• 1! = Q ^ 2, i = 0)

A H

R at the time of

R ⁴ R ⁴

I Ha α-Gen-Dai, Mesylation, I

ΟΗ ΟΗ —— "Α

Or tosylation-L].

(Rj- L ¹ when the ί = 0)

_ Chlorination or-

A— CH, A- CH ₂ C1 (Br)

. Bromination (when i = 0 and R ⁴ = H — L ¹ ) (Cl2, NCS, NBS, etc.)

[Wherein each symbol has the same meaning as described above. ] Reaction formula (κ)

(In the case of = Q ₂ , i ^ l)

R ²

A

O

Former

AC (R ² ) HC (R ³ ) H-hCCH _? OH

1) Hz / Pd—. etc

2) LiAlH ₄ or BH ₃ etc.

1-2

(i≥2 force; Ri—OH when R ⁴ = H) *) Chem.Ber., 95, 581 (1962), etc.CH _:

'3— _D 4

(Rj— OH when i = l and RR ⁴ = H) [Wherein each symbol has the same meaning as described above. ]

A—L ⁴ (where L ⁴ represents a halogen atom (a chlorine atom, a bromine atom, an iodine atom, etc.) among the compounds represented by the general formula (12), which are intermediates for producing the compound of the present invention). The compound represented by the formula (1) can be a commercially available compound, or can be produced, for example, by the method of the reaction formula (X).

Reaction formula (X)

1) Diazotization

A—Wind AL ⁴

2) CuC] or CuBr etc.

[Wherein, A and L ⁴ represent the same meaning as described above. ]

Compounds represented by the above general formula (11) and compounds represented by the general formulas (13) and (15), which are intermediates for the production of the compound of the present invention, can be produced, for example, by the reaction scheme

(XI) to (xm).

Reaction formula (XI)

R ⁴

D then B ^J

OH + HO-Y _W -OCH ₂ CH = CX ₂

(Four)

"1 R *

K protection

HB ¹ CH-OY ₁₀ -OCH ₂ CH = CX ₂

R ³ when Bi NH or 0

(Chemical 15; Bi-O (13))

((13); Chemical formula 15 = = 0) ((15)

(In (11)

[Wherein each symbol has the same meaning as described above. ]

*) J. Amer. C em. Soc., 33, 440 (1905) / JP95 / 02320

Reaction formula (π)

General formula (4)-

R = 7fiS¾ with ⁴ units

Agent I

D ^s 0-jC- CH-L is ^ Doo CH-L

When

R ³ ίΩ potassium, etc.) R ³

1-1 (potassium separation, etc.)

(For example, D ⁷ = C _E ¾C RI (eg, D ⁶ -acetal deprotection, deprotection,

OH-MeOH, etc.)

R ²

(13) β vit I

OHC † CK: HOY ₁₀ -OCH ₂ CIH: ¾

(= 0 in (11)) (NaB etc.)

1-1 halogenated (S0C1 _2, etc.),

Meshi-dani (sCl Et ₃ N, etc.)

Or

Toshi Whi (Ding sCl / E N, etc.)

(15) * ιli: Trifuenino Suhuin-Jetchinore

Hazoji turtle Us

[Wherein, Ms represents a mesyl group, Ts represents a tosyl group, D ⁵ represents an alcohol protecting group (eg, benzoyl group, etc.), and D ⁶ represents a formyl group protected group (eg, acetal). represents a group), L is Y ₁₀ represents a hydroxyl group or ^{^{^{L 1, R 2, R 3}}} , R 4, X, L 1 and i are as defined above. ] / 02320

Reaction formula (xm)

General formula (4)

L ^1- (CH ₂ ) _i -CH ₂ — L ^]

(Carbonated room, etc.)

L ¹ - (CH ₂₎ i one _{_{_{CH 2 - 0 -Y 10 -OCH 2}}} CH = CX

(In the general formula (15), R ² = = H)

[Wherein each symbol has the same meaning as described above. ]

The compound represented by the general formula (17) is, for example,

(XIV).

Reaction formula (XIV)

H ₂ NN¾ ¾tOH Heating: 3 flows

20

[Wherein each symbol has the same meaning as described above. ]

Examples of the pests against which the compound of the present invention exerts a controlling effect include the following.

Hemiptera pests

Black beetle power, brown beetle power, mosquitoes such as brown planthoppers, leafhoppers such as black leafhoppers, leafhoppers such as white leafhoppers, aphids, stink bugs, whiteflies, scale insects, hornworms, psyllids

Lepidoptera pests

White moths, such as Nikameiga (Nikameigayu), Kobunomeika, Noshimekokuga, etc. «5 ：: ^ ソ j Toma r? Ko k rt =) k -H '^ tT \ = J kn ゥ, Singing moths, Leaf moths, Doga moths, Pectinia, Agrothis spp., Heliothis spp., Konaga, Iga, Koiga etc.

Diptera pests

House powers such as akaie and kogatakaie powers, falcons such as anetaishima power, and hystodia powers, anopheles powers such as shinahamadara power, house flies such as musurika, housefly, oenfly, blowflies, and house flies. , Fly, onion flies, etc., fruit flies, flies, flies, flies, buchus, flies, etc.

Coleoptera pests

コーン Corn worms such as corn root worms and southern corn root worms; Scarabaeids such as Douganebuui and Himekogane; CT / JP95 / 02320

Tenebrion beetles such as Menome beetle and Pterodactyla beetle, Beetle beetles such as Kisujino z, mimushi, and beetle, etc.バガリ等

Reticulate pests

Chinese cockroaches, black cockroaches, red cockroaches, flying cockroaches, spring cockroaches, etc.

Pteratoid pests

Southern yellow thistle, yellowtail thistle, etc.

Hymenoptera pests

Orthoptera, insects such as wasps, wasps, wasps, and wasps

Kera, grasshopper, etc.

Insect pests

^^

Lice pests

Firefly, Kesira ^

Isoptera pests

Yamato termite, house termite, etc.

Harmful insects such as

Mites

Plant parasitic mites such as Nami-Namidani, Mandarin spider mite, Nisenami-Namidani, and Apple spider mite; Animal-parasitic ticks such as Dermatophagoides, indoor dust mites, etc. Harmful mites such as

It is also effective against pests that have developed resistance to existing pesticides. When the compound of the present invention is used as an active ingredient of an insecticide or acaricide, it may be used as it is without adding any other components, but usually, a solid carrier, a liquid carrier, a gaseous carrier, a bait. And surfactants and other adjuvants, if necessary, for oils, emulsions, wettable powders, flowables, powders, aerosols, aerosols (fogging, etc.), poison baits, etc. Formulated for use.

These preparations usually contain the present compound as an active ingredient in an amount of 0.01 to 95% by weight.

Examples of solid carriers used in the formulation include clays (such as clay ore clay, diatomaceous earth, synthetic hydrous silicon oxide, bentonite, fupasami clay, acid clay, etc.), talcs, ceramics, and others. Fine powders or granular materials such as inorganic minerals (cericite, stone, sulfur, activated carbon, calcium carbonate, hydrated silica, etc.) and chemical fertilizers (ammonium sulfate, phosphorus ammonium, ammonium nitrate, urea, salt ammonium, etc.) Examples of the liquid carrier include water, alcoholic water (methanol, ethanol, etc.), ketones (acetone, methylethylketone, etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, methylnaphthalene, etc.), Aliphatic hydrocarbons (hexasis, cyclohexane, kerosene, diesel, etc.), esters (ethyl acetate, butyl acetate, etc.) Ryls (acetonitrile, isoptyronitrile, etc.), ethers (diisopropyl ether, dioxane, etc.), acid amides (N, N-dimethylformamide, N-dimethylacetamide, etc.), halogenated carbonized Hydrogens (dichloromethane, trichloroethane, carbon tetrachloride, etc.), dimethyl sulfoxide, vegetable oils such as soybean oil, cottonseed oil, etc. are listed. As a gaseous carrier, that is, a propellant, for example, freon gas, butane gas, LPG ( Liquefied petroleum gas), dimethyl ether, carbon dioxide, etc. / 02320

You.

Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylenates thereof, polyethylene glycol ethers, polyhydric alcohol esters, and sugar alcohols. Derivatives and the like. Examples of pharmaceutical adjuvants such as fixatives and dispersants include casein, gelatin, polysaccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, sugars, synthetic water-soluble Molecules (polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acids, etc.), and the like. Examples of stabilizers include PAP (isopropyl acid phosphate) and BHT (2,6-di-tert-butyl-4-methylfunninol). ), BHA (a mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenyl), vegetable oils, mineral oils, surfactants, fatty acids or esters thereof.

Examples of bait baits include bait ingredients such as cereal flour, vegetable essential oils, sugar, and crystalline cellulose; antioxidants such as dibutylhydroxytoluene and nordihydrologiaretic acid; preservatives such as dehydroacetic acid; Powders, etc., and inducing flavors such as cheese flavors, onion flavors and the like.

The preparation thus obtained is used as it is or diluted with water or the like. Also mixed with or mixed with other insecticides, nematicides, acaricides, fungicides, herbicides, plant growth regulators, synergists, fertilizers, soil conditioners, animal feed, etc. It can also be used at the same time without using.

Examples of the insecticide, nematicide, and acaricide to be used include, for example, funiniothione [0,0-dimethyl 0- (3-methyl-412-trophenyl) phosphorothioate], phenicion [〇, 〇一] Dimethyl p- (3-methyl-1- 1- (methylthio) phenyl) phosphorothioate], diazinon [〇, 0-diethyl- 0-2-isopropyl-16-methylpyrimidine-14-ylphosphorothioate], chlorpyrifos [0, 0-jetyl-1 0-3,5] , 6-trichloro-2-pyridyl phosphorothioate], acephate [0, S-dimethyl acetyl acetyl phosphoramido thioate], methidathion [S-2,3-dihidro 5-methoxy 2-oxo) 1,3,4-thiadiazol-3-ylmethyl 0,0-dimethylphosphorodithioate], disulfotone [0.0—getyl S-2-ethylthioethyl phosphorothioate], DD VP [2,2-dichlorovinyl dimethyl phosphate], sulphophos [0-ethyl 0-4 (methylthio) phenyl S-propylphosphorodithioate], cyanophos [0-4 4-cyanophen] 0,0-Dimethylphosphorothioate], dioxabenzophos [2-methoxy-14H-1,3,2-benzodioxaphosphinin-12-sulfide], dimethoate [0,0-dimethyl] S- (N-methylcarbamoylmethyl) dithiophosphonate], phentoate [ethyl 2-dimethoxyphosphinothiothiothio (phenyl) acetate], malathion [Jetyl (dimethoxyphosphinothiothiothio) succinate], trichlorfon [dimethyl2] , 2,2-Triclo-l-l-hydroxyl shetylphosphonate], azinphos-methyl [S-3,4-dihydro 4- 4-oxo-1,2,3-benzotriazine-3-ylmethyl 0,0-dimethyl Phosphorodithioate], Monochrome Tophos [Dimethyl (E) -1-methyl-12- (methylcarbamoyl) vinyl phosphate] Organic phosphorus compounds such as ethion [0, 〇, 〇 ', 〇'-tetraethyl S, S'-methylenebis (phosphorodithioate)], B PMC (2-sec-butylphenylmethylcarbamate) ), Benfracarb [ethyl 2-(2,3-dihydro 2.2-dimethylbenzofuran 1-7-iloquin carbonyl (methyl) aminotio]-1-isop Mouth pill-1 3-alaninate], Proboxil [2-isopropoxyphenyl-methyl carbamate], Carbosulfan [2,3-dihydro 2,2 monodimethyl 7-benzo [b] furanyl N- N-methylcarbamate dibutylaminotyl, potassium valvalyl [1-naphthyl-N-methylcarbamate], mesomyl [S-methyl-N-[(methylcarbamoyl) oxy] thioacetate imidate], ethyl thiophene Carp [2- (ethylthiomethyl) phenylmethylcarbamate], aldicarb [2-methyl-2- (methylthio) propionaldehyde 0-methylcarbamoyloquin], oxaminole [I \ ', N-dimethyl-2-methylmethylcarbamoyloxy Simino 2— (Methylthio) acetamide], Phenothiocalp [S—4-Phenoxyptyl Γ \ ', N—Dimethylthioca Carbamate-based compounds such as [bamate], ethonin block, [2- (4-ethoxyphenyl) -1-2-methylpropyl-13-phenoxybenzyl ether], and fenvalerate [(RS) -histocyano-3-phenoquinbenzyl] (RS) —2— (4-chlorophenyl) -1-methylbutyrate], esfenvalerate [(S) —N-cyano-13-phenoxybenzyl (S) —2— (4— Phenyl) -3-methylbutyrate], fenpronothrin [(RS) -a-cyano 3-phenoxybenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate], cyperme Tolene [(RS) -Hydroxy 3- 3-phenoxybenzyl (1 shaku 5,31 ^ 3) -3- (2,2-dichlorovinyl) -1,2,2-dimethylcyclopropanecarboxylate] , Permethrin [3-phenoxybenzyl ( 1 shaku 5, 3 shaku 3) —3- (2,2-dichlorovinyl) -1,2,2-methylcyclopropanecarboxylate], xylotrin [(RS) -a-cyano-13-phenoki) Cibenzyl (Z) — (1 RS) —cis—3— (2-chloro-3,3,3-trifluoroprop-1-enyl) -1,2,2-dimethylcyclopropanecarboxylate], deltamethrin [(S) — α-Cyanol 3-phenoxybenzyl (1R, 3R) —3- (2,2-dibromovinyl) -1,2,2-dimethylcyclopropanecarboxylate], Cyclic mouth prothrin [(RS) —N-Cyanaw 3 —Phenoxybenzyl (RS) — 2,2-Dichloro-1- (4-ethoxyquinpenyl) cyclopropanecarboxylate], fulvalinate (1-cyano 3-phenoxybenzyl Ν— (2-chloroopen-na, α , — Trifluoro-ρ-trinole) -D-variate), biphenyl (2-methylbiphenyl-3-ylmethyl) (Z) — (1 RS) -cis-3 -— (2-chloro-3,3,3 — Trifluoroprop-1-enyl) -1,2,2-dimethylcyclopropanecarboxylate, acrinasulin C [lR- {la (S *), 3α (Ζ)}]-2,2-dimethyl-1- 3— [3—one piece — ^ 2 2 2 one piece “ ⁷ holes” ^ ^π -one f Ηヽ、, 1-probenyl] cyclopropanecarboxylic acid (S)-(a)-cyano (3-phenoxyphenyl) methyl ester, 2-methyl-12-(4-bromodifluoromethoxyphenyl) propyl (3- Phenoxybenzyl) ether, tralomethrin [(1 R, 3 S) 3 RS) (Γ, Γ, 2 ', 2'-tetrabromoethyl)]-2,2-dimethylcyclopropanecarboxylic acid (S) Pyrethroid compounds, such as chloropropane-3, -phenoxybenzyl ester], silafluophane [4-ethoxyphenyl [3- (4-fluoro-3-phenoxyphenyl) propyl] dimethylsilane], and buprofidine (2 — Thiadiazine derivatives such as tert-butylimino 3- 3-isopropyl- 15-phenyl-1,3.5-thiadiazinan-4-one) and imidacloprid (1- (6-chloro-3-pyridylmethyi) 2) 2-Troymidazolidin derivatives such as 1-N--2-tromidazolidine-12-indeneamine), cartap (S, S '-(2-dimethylaminotrimethylene) bis (thiocarbamate)), thiocyclam [ N, N—Dimethyl 1.2.3—Tritian 5-ylamine], Bensultad Nereistoxin derivatives such as [S, S'—2-dimethylamino trimethylene di (benzenethiosulfofolate)], N-cyano N'-methyl-N '-(6-chloro-3-pyridylmethyl) acetamidine N-cyanoamidine derivative, end-sulfan [6,7,8,9,10,10-hexachloro-1,5,5a, 6,9,9a-hexahydrol 6,9-methanol 2,4,3- Benzodioxachepinoxide], BHCC1, 2, 3, 4.5, 6-hexachlorocyclohexane), 1,1-bis (chlorophenyl) -1.2.2-2 Chlorine such as trichloroethanol Chloroflurazuron [1- (3,5-dichloro-4-1 (3-chloro-5-trifluoromethylpyridine-12-yloxy) phenyl) -1-3- (2,6-difluoro) Benzoyl) ゥ rea], tefluvenzuron [1— (3,5—dichro 2,4-Difluorophenyl) 1 3- (2,6-difluorobenzobenzene) rare, Flufenoxuron [1- (4- (2-chloro-4-4-trifluoromethylphenoxy)] Benzoylphenyl urea compounds such as 2-fluorophenyl] -3- (2,6-difluorobenzoyl) rea, amitraz [N.N '— [(methylimino) dimethylyl] di-1,2,4-xylidine] Formamide derivatives such as chlordimeform [Ν '-(4-chloro-2-methylphenyl) -1-Ν, Ν-dimethylmethinimidamide], diafentiuron [Ν- (2,6-diisopropyl-1-4) Thiourea derivatives such as — (phenoxyphenyl) -N′—tert-butylcarbodiimide), bromopropylate [isopropyl 4.4′-dibromobenzylate], tetradiphone [4 1,4-chlorophenyl 2,4,5-tri] Chlorophenyl Horn), quinomethionate [S, S-6-methylquinoxaline-2,3-diethyldicarbonate], propargate [2- (4-tert-butylphenoxy) cyclohexyl propyl-2-yl sulfite ], Fenptatin oxide [bis [tris (2-methyl-2-phenylpropyl) tin] Hexoxide], hexithizox [(4RS, 5RS) —5- (4-chlorophenyl) -N-chlorohexyl 4-methyl-2-oxo-1,3-thiazolidin-13-carboxamide], chloro Fuentezin [3,6-bis (2-chloro phenyl) -1,2,4,5-tetrazine, pyridatiobene [2-tert-butyl 5- (4-tert-butylbenzylthio) -1 4-chloro] Pyridazine-1 (2H) -one], fenpyroximate [tert-butyl (E) -4-1 [(1,3-dimethyl-5-phenoxypyrazole-14-yl) methyleneaminooxymethyl] benzoate] , Debufenpyrad [N-4-1-tert-butylbenzyl) -14-chloro-3-ethyl-11-methyl-15-pyrazolecarboxamide, polynactin complex [tetranactin, dinactin, trinactin], milbe Mectin, Abe Mectin, ivermectin, azadirachtin [AZAD], pyrimidifene [5-chloro-N- [2- {4- (2-ethoxyxethyl) -1,2,3-dimethylphenyloxy] ethyl] -6-ethylpyrimidin 4 monoamine and the like.

When the compound of the present invention is used as an insecticide or acaricide for agriculture, the application rate is usually 0.1 lg to 100 g per 10 ares, and the emulsion, wettable powder, flour and the like are diluted with water. If used, the application concentration is usually 0. IPP n! ~ 500 ρρπι, 'Granules, dusts, etc. are applied as is without any dilution. When used as an insecticide or acaricide for prevention of epidemics, emulsions, hydrating agents, flowables, etc. are usually treated with water at a pH of 0.1%! Apply it after diluting to ~ 50 Oppm. Apply oils, aerosols, aerosols, poison baits, etc. as they are. All of these application rates and concentrations vary depending on the type of preparation, application time, application place, application method, type of pest, degree of damage, etc., and can be increased or decreased without being affected by the above range. Or can be. Hereinafter, the present invention will be described in more detail with reference to Production Examples, Formulation Examples and Test Examples. It explains, but the present invention is not limited to these examples _e

First, Production Examples of the compound of the present invention will be described.

Production Example 1

Production of the following compound (13) by (Production method B)

2 Stir at room temperature with a mixture of 0.2 lg of monochloro-5- (3,3-dichloro-2-brodinyloxy) naphthol, 0.2 lg of potassium carbonate and 20 ml of N, N-dimethylformamide. Meanwhile, a solution of 0.23 g of 2,3-dichloro-5- (trifluoromethyl) pyridine and 5 ml of Ν, 1 \ -dimethylformamide was added dropwise. After stirring at room temperature for 7 hours, the reaction solution was poured into ice water and extracted twice with 50 ml of getyl ether. The ether layers were combined, washed with water, dried over anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography to give 2-chloro-1- (3-chloro-5- (trifluoromethyl) -1-pyridyloxy) -1-5- (3,3-dichloro-1-propenyloxy). 0.2 lg of naphthalene was obtained.

43% yield

m. P. 126. 1 ° C

Production Example 2

Production of the following compound (18) by (Production method A)

To a solution of 5- (3,3-dichloro-12-propenyloxy) -11-naphthonone 0.30 g, 3-benzyloxybenzyl alcohol 0.24 g and triphenylphosphine 0.29 g in 10 ml of tetrahydrofuran, A solution of 0.22 g of diisopropylpropylazodicarboxylate in 5 ml of tetrahydrofuran was added dropwise with stirring at room temperature. After stirring at room temperature for 24 hours, the reaction solution was concentrated to give a residue. This residue was subjected to silica gel chromatography to obtain 11- (3-benzyloquinbenzyloxy) -1- (3,3 0.28 g of dichloro-2-provenyloxy) naphthalene was obtained.

Yield 54%

no ²⁴ - ⁵ 1. 61 14

Production Example 3

Production of the following compound (17) by (Production method A)

5- (3,3-dichloro-1--2-propylenyl) -1-naphthol 0.30 g, 0.25 g of 4-phenyloxybenzyl alcohol and 0.29 g of triphenylphosphine were dissolved in a solution of 10 ml of tetrahydrofuran. A solution of 0.22 g of diisopropylpropylazodicarboxylate in 5 ml of tetrahydrofuran was added dropwise with stirring at room temperature. After stirring at room temperature for 24 hours, the reaction solution was shrunk to obtain a residue. The residue was subjected to silica gel chromatography to obtain 0.14 g of 1- (3,3-dichloro-12-probenyloxy) -15- (4-phenoxybenzyloxy) naphthalene.

Yield 28%

no ²⁴ - ⁵ 1. 6352

Production Example 4

Production of the following compound (9) by (Production method B)

5- (3,3-dichloro-1- 2-propenyloxy) -111 naphth tonole 0.40 g, potassium carbonate 0.23 ^{: /} , N-dimethylformamide 20 ml mixture While stirring at room temperature, a solution of 0.29 g of 3- (trifluoromethyl) benzyl chloride and 5 ml of N-dimethylformamide was added dropwise. After stirring at room temperature for 7 hours, the reaction solution was poured into ice water and extracted twice with 50 ml of getyl ether. The ether layers were combined, washed with water, dried over anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel chromatography to give 1,3- (3,3-dichloro-2-provenylo). 20

0.40 g of (xy) -5- (3- (trifluoromethyl) benzyloxy) naphthalene was obtained.

Yield 62%

m.p. 73.7 ° C

Production Example 5

Production of the following compound (10) by (Production method B)

To a mixture of 5- (3,3-dichloro-2-propenyloxy) -11-naphthonone 0.40 g, lithium carbonate 0.23 g and N, N-dimethylformamide 2 Oml at room temperature with stirring. A solution of 0.37 g of 3-bromobenzylbutane and 5 ml of N, N-dimethylformamide was added dropwise. After stirring at room temperature for 7 hours, the reaction solution was poured into ice water and extracted twice with getyl ether 5 Oinl. The ether layers were combined, washed with water, dried over anhydrous magnesium sulfate, and then condensed to obtain a crude product. This crude product was subjected to silica gel chromatography to obtain 0.49 g of 1- (3-bromobenzyloxy) -15- (3,3-dichloro-12-propynyloxy) naphthalene.

75% yield

m.p. 84.δ ° C

Production example 6 '

Production of the following compound (3) by (Production method B)

A mixture of 7- (3,3-dichloro-2-propionyloxy) -1-naphthonone 0.40 g, lithium carbonate 0.3 lg and N, N-dimethylformamide 20 ml was stirred at room temperature under stirring. A solution of 0.39 g of 3-promo-2-chloro-5- (trifluoromethyl) pyridine and 5 ml of N, N-dimethylformamide was added dropwise. After stirring the mixture at room temperature for 7 hours, the reaction solution was poured into ice water and extracted twice with 50 ml of getyl ether. Combine the ether layers and add water The extract was washed, dried over anhydrous magnesium sulfate, and concentrated to obtain a crude product. This crude product was subjected to silica gel chromatography to give 0.55 g of 2- (3-bromo-15- (trifluoromethyl) -12-pyridyloxy) -17- (3,3-dichloro-2-brodinyloxy) naphthalene. Obtained.

75% yield

n _D ²⁶ - ⁰ 1.6005

Production Example 7

Production of the following compound (1) by (Production method C)

A mixture of 5- (3-chloro-5- (trifluoromethyl) -1-pyridylloquine) -11-naphthol 0.40 g, potassium carbonate 0.20 g and N, N-dimethylformamide at room temperature with stirring. A solution of 0.19 g of 1,1,3-trichloropropene and 5 ml of N, N-dimethylformamide was added dropwise. After stirring at room temperature for 7 hours, the reaction solution was poured into ice water and extracted twice with 50 ml of getyl ether. The ether layers were combined, washed with water, dried over anhydrous magnesium sulfate, and concentrated to obtain a crude product. This crude product was subjected to silica gel chromatography, and 0.4 g of 1- (3-chloro-5- (trifluoromethyl) -12-pyridyloxy) -1-5- (3,3-dichloro-2-pronenyloxy) nastalen was obtained. Obtained.

76% yield

m.p. 82.7 ° C

Production Example 8

Production of the following compound (24) by (Production method B)

0.24 g of 2,3-dichloro-5- (trifluoromethyl) pyridine, 0.30 g of 5- (3,3-dichloro-12-propenyloxy) -1,2,3,4-tetrahydro-11-naphthol, 0.23 g of lithium carbonate and N, N-dimethyl A mixture of 2 Oml of formamide was stirred at 80 ° C for 6 hours. The reaction solution was poured into ice water, and extracted twice with 50 ml of getyl ether. The ether layers were combined, washed with water, dried over anhydrous magnesium sulfate, and concentrated to obtain a crude product. This crude product was subjected to silica gel column chromatography to give 1- (3-chloro-5- (trifluoromethyl) -12-pyridyloxy) -1-5- (3.3-dichloro-2-propinyloxy) -1 1,2,3,4-Tetrahydronaphthalene 5 Omg was obtained.

Yield 10%

no ²⁵ - ⁰ 1. 5382

Production Example 9

Production of the following compound (31) by (Production method B)

5- (3,3-dichloro-2-provenyloxy) -1-1 naphthol 0.30 g, 1-promoter 3- (4- (trifluoromethoxy) phenoxy) propane 0.36 g, lithium carbonate 0.15 g and N- dimethylformamide mixtures § Mi de 5ml was poured into ice water and stirred for 2 hours was _c reaction solution at room temperature and extracted twice with Jechi Rue one ether 5 Οπιΐ. The ether layers were combined, washed with water, dried over anhydrous magnesium sulfate, and dried to obtain a crude product. This crude product was subjected to silica gel column chromatography to obtain 0.34 g of 1- (3,3-dichloro-2-provenyloxy) -1-5- (3- (4- (trifluoro (methoxy) fuunoxy) propoxy) naphthalene. Was.

Yield 58%

m.p. 77.8 ° C

Production Example 10

Production of the following compound (34) by (Production method A)

2-chloro-5- (3,3-dichloro-2-propenyloxy) -1-na To a mixture of 0.91 g of phthalone, 0.74 g of 3- (4- (trifluoromethyl) benzoylamino) -1-1propanol, 0.79 g of triphenylphosphine and 1 Onl of dichloromethane, was stirred under ice temperature at an ice temperature. Then, 0.59 ml of diisopropylazodicarboquinate was slowly added dropwise. After stirring at room temperature for 24 hours, the reaction solution was concentrated to obtain a residue. The residue was subjected to silica gel column chromatography to give 2-chloro-5- (3,3-dichloro-1--2-propenyloxy) -1-1 (3- (4- (trifluoromethyl) benzoylamino). 0.6 lg of propyloxy) naphthalene was obtained.

Yield 38%

m.p. 1 08.8 ° C

Next, some specific examples of the compound of the present invention are shown together with compound numbers.

(1) 1- (3-Chloro-5- (trifluoromethyl) -1-pyridyloxy) -1-5- (3,3-dichloro-12-propenyloxy) naphthalene

m.p. 82.7 ° C

(2) 2- (3-Chloro-5- (trifluoromethyl) -1-2-pyridyloxy) -17- (3.3-Dichloro-1--2-propidinoloquine) naphthalene

no ²⁶ - ⁰ 1. 5952

(3) 2- (3-Bed π mode 5- (Bok Rifuruoromechiru) one 2-pyridyl Jiruo Kin) eleven 7- (3, 3-dichloro-one 2-propenyl Niruokishi) naphthalene no ²⁶ - ⁰ 1. 6005

(4) 1,5-bis (3,3-dichro-2--2-propenyloxy) naphthalene

m.p. 96.9 ° C

(δ) 1- (3,3-dibu-mouth 2- 2-proenyloxy) -1- 5- (3,3-dichloro-2-proenyloxy) naphthalene mp 109.4 ° C

(6) 1- (2-cyclobenzyloxy) -1-5- (3,3-dichloro-2-brodinoxy) naphthalene m.p. 106.8 ° C

(7) 11- (3-chlorobenzyloxy) -1-5- (3,3-dichloro-2-propinyloxy) naphthalene m.p. 84.5

(8) 1- (4-benzyloxy) -1-5- (3.3-dichloro-2-propionyloxy) naphthalene m.p. 107.0 ° C

(9) 1- (3,3-dichloro-2-propenyloxy) -1- (3-tri

m. p. 73.7. C

(10) 11- (3-Bromobenzyloquin) -1-5- (3,3-dichloro-2-propenyloxy) naphthalene m.p. 84.5. C

(11) 1- (3-bromo-5- (trifluoromethyl) 1-2-pyridyloquine) -5- (3, .3-dichloro-12-propenyloxy) naphthalene

in.p. 101.2 ° C

(12) 1- (4-bromobenzyloxy) -1-5- (3,3-dichloro-2-propenyloxy) naphthalene m.p. 8 δ .5 ° C

(13) 2-Chloro-1-(3-chloro-5- (trifluoromethyl) -1-pyridylloquine) -1-5- (3,3-dichloro-2-propidinyloxy) naphthalene mp 126.1 C

(14) 1- (3-bromo-5- (trifluoromethyl) -1-pyridyloxy) -1-chloro-5- (33-dichloro-12-propenyloxy) naphthalene

m.p. 129.3 ° C

(15) 1- (4-bromobenzyloxy) 1-2-chloro 5- (3,3-dichloro-2-propenyloxy) naphthalene

m.P. 101.4 ° C

(16) 2,7-bis (3,3-dichloro_2-provenyloxy) naphthalene

(17) 1- (3,3-dichloro-2-propenyloxy) -1 5- (4-phenoxybenzyloxy) naphthalene

o ²⁴ - ⁵ 1.6352

(18) 1- (3-benzyloquinbenzyloxy) -1-5- (33-dichloro-2-provenyloxy) naphthalene

η 【) ²⁴・⁵ 1.6114

(19) 2- (3,3-Dichloro-2-proenyloxy) -17- (4-phenoxybenzyloxy) naphthalene

m.p. 84.6 ° C

(20) 2- (3-Benzyloxybenzyloquine) -7- (3,3-dichloro-2--1-propynyloxy) naphthalene

m.p. 92.δ ° C

(21) 2- (3-chloro-5- (trifluoromethyl) -1-2-pyridyloxy) -1-6- (3,3-dichloro-2-propenyloxy) naphthalene mp 78.4 ° C

(22) 1-1-2- (3--1-5- (trifluoromethyl)-1-pyridyloxy)-7-(3,3-dichloro-2-propidinyloxy) naphthalene

m.p. 132.9 ° C

(23) 1-chloro-2- (3-chloro-1-5-trifluoromethyl) -2-pyridyloxy-1-6- (3,3-dichloro-2-propenyloxy) naphthalene

m.p. 90.3 ° C

(24) 1- (3-chloro-5- (trifluoromethyl) 1-2-pyridyloxy) -5- (3.3-dichloro-2-propinyloxy) -1,2.3,4-1 tetrahydrodronaphthylene

no ²⁵ - ⁰ 1.5382

(25) 1- (3-Chloro-5- (trifluoromethyl) 1-2-pyridyloxy) 1-14-1 (3,3-Dichloro-2-propidinoloquine) naphthalene

(26) 1- (3-chloro-5- (trifluoromethyl) 1-2-pyridylquine) -1 4- (3,3-dibutoxy 2-propidinyloxy) naphthalene

'm.p. 76.4 ° C

(27) 1- (3,3-dichloro-1-2-pronenyloxy) -5- (2- (4- (trifluoromethyl) phenyl) ethoxy) naphthalene

m.p.δ 7.0 ° C

(28) 1- (3,3-dichloro-2-proenyloxy) -1- (4- (4- (trifluoromethylinole) phenyl) butyloxy) naphthalene

n _D ²⁵ ° 1.5691

(29) 2-chloro-1-5- (3.3-dichloro-2-propenyloxy) -1 1- (2-((4- (trifluoromethyl) phenyl) ethoxy) naphthalene mp 66.6 ° C

(30) 2- chloro 5- (3, 3-dichloro 2- Purobe Niruokishi) Single 1 i (2- (4 one (triflate Ruo B methyl) phenyl) Buchiruokin) naphthalene no ²⁵ - ⁰ 1.5747

(31) 1- (3,3-Dichloro-2-provenyloxy) -1-5- (3- (4- (trifluoromethyl) phenyloxy) propinyloxy) naphthalene

m.p. 77.8 ° C

(32) 2-chloro-5- (3.3-dichloro-2-propidinoxy)

1 — — C Λ — ί k tl one, then + π-· ≠-one-no soil-'one ⁰ η レ⁰ , then + soil,' _μ one

n _D ²⁵ - ⁰ 1.5695

(33) 3- (5- (3,3-Dichloro-2-proenyloquin) -1-1-naphthoxy) propyl 4- (trifluoromethoxy) benzoate

m.p. 102.9 ° C

(34) 2-Chloro-5- (3,3-dichroic-2-1-2-propenyloxy) -1- (3- (4- (trifluoromethyl) benzoylamino) propyloquin) naphthalene

ni.. 108.8 ° C

(35) 1- (3.3-dichloro-2-proenyloxy) -1-5- (3- (5- (trifluoromethyl) -1-2-pyridyloxy) propyloquin) naphthalene

m.p. 92.3 ° C

(36) 2-Chloro-5- (3,3-dichro-2-1-2-proenyloxy) 1- (3- (5-trifluoromethyl) -1-2-pyridyloxy) propyloxy) naphthalene

(37) 11- (3,3-dichloro-2-brodinoxy) -1-5- (4- (4- (trifluoromethyl) phenoquine) butyloxy) naphthalene

(38) 2-Chloro-5- (3,3-dichloro-2-provenyloquine) 1-1- (4- (4- (trifluoromethoxy) phenyloxy) butylyloxy) naphthalene

(39) 1- (3,3-dichloro-2-pronenyloxy) -1 5- (3- (4- (4- (trifluoromethyl) benzoylamino) propyloquin) naphthalene

(40) 1- (3,3-Dichloro-2-propenyloxy) -1-5- (4- (4- (trifluoromethyl) benzoylamino) butyloxy) naphthalene

(41) 2-Chloro-5- (3.3-dichro-2--1-pronenyloxy) -111 (4- (4- (trifluoromethyl) benzoylamino) butyoloquine) naphthalene

Next, production examples of the intermediates represented by the general formulas (2) and (6) will be described. Intermediate production example; L '

(Production of Intermediate Compound 3))

A mixture of 25 g of 2,7-dihydroxylphthalene, 43.lg of potassium carbonate and 250 ml of N.N-dimethylformamide was stirred at room temperature while stirring at room temperature with 22.7 g of 1,1,3-trichloropropene and N, N. A mixed solution of 50 ml of N-dimethylformamide was slowly added dropwise. After stirring at room temperature for 6 hours, the reaction solution was poured into a mixture of dilute hydrochloric acid and ice to neutralize, and extracted twice with 600 ml of getyl ether. Combine the ether layers, wash with water and dry over anhydrous magnesium sulfate / J 9S / 02320

Then, the mixture was concentrated to obtain a crude product. This crude product was subjected to silica gel column chromatography to obtain 9.8 g of 7- (3,3-dichloro-1--2-provenyloxy) -1-naphthonone.

Yield 37%

m.p. 94.δ ° C

Intermediate Production Example 2

(Production of intermediate compounds 1) and 2))

To a mixture of 25 g of 1,5-dihydroxylphthalene, 43.lg of carbonated rhodium and 25 Oml of N, _N -dimethylformamide, 22.7 g of 1,1,3-trichloropropene and N A mixed solution of 50 ml of N, dimethylformamide was slowly added dropwise. After stirring at room temperature for 6 hours, the reaction solution was poured into a mixture of dilute hydrochloric acid and ice to neutralize, and extracted twice with 600 ml of getyl ether. The ether layers were combined, washed with water, dried over anhydrous magnesium sulfate, and then concentrated to obtain a crude product. This crude product was subjected to silica gel column chromatography to obtain 8.5 g of 5- (3,3-dichloro-2-propenyloxy) -11-naphthol (intermediate compound 1)).

Yield 20%

m.p. 122.7 ° C ''

Add 0.5 ml of N, N-dimethylformamide to a mixture of 1.35 g of 5- (3,3-dichloro-12-propenyloxy) -11-naphthol and 30 ml of carbon tetrachloride, and add While stirring, a solution of 0.54 g of tert-butyl hypochlorite dissolved in 5 ml of carbon tetrachloride was slowly added dropwise. After 24 hours, the reaction solution was poured into water, and the organic layer (carbon tetrachloride) was separated. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated to obtain a crude product. The crude product was subjected to silica gel column chromatography to give 2-chloro-5- (3,3-dichloromethane. There was obtained 0.87 g of lolo-2-provenyloxy) -11-naphthol (intermediate compound 2)).

Yield 51%

ZH-NMR (CDC13 ₃ TMS)

6 (ρρπι): 4.83 (2H, d). 5.98 (lH, s), 6.27 (lH.t), 6.82 (lH, d), 7.34 ~ 7.44 (2H, m), 7.75 ~ 7.84 (2H ' m) Reference production example 1

1, 5-dihydroquinone 1, 2.3, 4-tetrahydrodronaphthalene 5.0 g, potassium carbonate 5. lg and N, N-dimethylformamide 100 ml while stirring at room temperature A mixed solution of 4.9 g of 1,1,3-triclopropene and N, N-dimethylformamide 2 Offil was slowly added dropwise. After stirring at room temperature for 6 hours, the reaction solution was poured into ice water and extracted twice with 20 ml of getyl ether. The ether layers were combined, washed with water, dried over anhydrous magnesium sulfate, and concentrated to obtain a crude product. This crude product was subjected to silica gel column chromatography to obtain 6.34 g of 5- (3,3-dichloro-2-propenyloxy) -1,2,3,4-tetrahydro-11-naphthol.

76% yield

m.p. 67.0 ° C

Specific examples of the intermediate compounds represented by the general formulas (2) and (6) are described below.

1) 5— (3,3-dichrochloride 2-propidyloxy) -1-11 naphthol m.P. 122.7 ° C

2) 2-Chloro-5- (3,3-dichloro-2-propenyloxy) -1-1 naphthol

5 (ppm): 4.83 (2H, d) .5.98 (lH, s), 6.27 (1H, t) .6.82 (lH'd), 7.34 ~ 7.44 (2H, m), 7.75 ~ 7.84 (2H , m)

3) 7— (3,3-Dichloro-2-provenyloxy) -1-2-naphthol m.P. 94.δ ° C

4) 6— (3,3-Dichloro-12-proenyloxy) -12-naphthol m.p. 117.0. C

5) 1—Black mouth 7— (3,3-Dichro mouth 1—Propenyloxy) 1—1 Naphthol

m.p. 82.1 ° C

6) 1—Black mouth 6— (3,3-Dichro mouth 1—Provenyloxy) 1—2-Naphthol

m.P. 98.0 ° C

Next, formulation examples are shown. In addition, parts represent parts by weight, and the compound of the present invention is represented by the above compound number.

Formulation Example 1,

Emulsion

10 parts of each of the compounds (1) to (41) of the present invention are dissolved in 35 parts of kynlen and 35 parts of dimethylformamide, and 14 parts of polyoxyethylenestyrylphenyl ether and 6 parts of calcium decylbenzenesulfonate are added thereto. Mix well with stirring to obtain each 10% emulsion.

Formulation Example 2

Wettable powder C / JP95 / 02320

20 parts of each of the compounds of the present invention (1) to (41) were mixed with 4 parts of sodium lauryl sulfate, 2 parts of calcium ligninsulfonate, 20 parts of fine powder of synthetic hydrous silicon oxide and 54 parts of diatomaceous earth. In addition, mix with a juice mixer to obtain each 20% wettable powder.

Formulation Example 3

Granules

To 5 parts of each of the compounds of the present invention (1) to (41), 5 parts of synthetic hydrous silicon oxide fine powder, 5 parts of sodium dodecylbenzenesulfonate, 30 parts of bentonite and 55 parts of clay are added and mixed with sufficient stirring. Then, an appropriate amount of water is added to the mixture, and the mixture is further stirred, granulated by a granulator, and dried by ventilation to obtain 5% granules of each.

Formulation Example 4

Powder

One part of each of the compounds of the present invention (1) to (41) is dissolved in an appropriate amount of acetone, 5 parts of synthetic hydrous silicon oxide fine powder, 0.3 part of PAP and 93.7 parts of clay are added, and the mixture is stirred and mixed with a juice mixer. Then, acetone is removed by evaporation to obtain 1% of each powder.

Formulation Example 5 '

Flowable agent

20 parts of each of the compounds of the present invention (1) to (41) and 1.5 parts of sorbitan trioleate are mixed with 28.5 parts of an aqueous solution containing 2 parts of polyvinyl alcohol, and finely powdered (particle size) with a sand grinder. 3), then add 40 parts of an aqueous solution containing 0.05 parts of xanthangam and 0.1 parts of aluminum magnesium silicate, further add 10 parts of propylene glycol, mix and mix, and suspend each in 20% water. A turbidity agent is obtained. Formulation Example 6

Oil

0.1 part of each of the compounds (1) to (41) of the present invention is dissolved in 5 parts of xylene in 5 parts of trichloroethane, and mixed with 89.9 parts of deodorized kerosene to obtain each 0.1% oil.

Formulation Example 7

Oily aerosol

An aerosol container was prepared by mixing and dissolving 0.1 part of each of the present compounds (1) to (41), 0.2 part of tetramethrin, 0.1 part of d-phenosulin, 10 parts of trichloroethane and 59.6 parts of deodorized kerosene. After filling with a valve part, 30 parts of a propellant (liquefied petroleum gas) is charged under pressure through the valve part to obtain each oil-based azole.

Formulation Example 8

Aqueous aerosol

0.2 parts of each of the compounds of the present invention (1) to (41), 0.2 parts of d-arrestrin, 0.2 parts of d-pheno'Jane, 5 parts of xylene, 3.4 parts of deodorized kerosene, and an emulsifier (ATMOS 300 (Atlas Chemical Co., Ltd.) The aerosol container is filled with 1 part mixed and dissolved and 50 parts of pure water, a valve is attached, and 40 parts of propellant (liquefied petroleum gas) is pressurized through the valve. Fill to obtain each aqueous azole.

Formulation Example 9

Mosquito coil

To 0.3 g of each of the compounds (1) to (41) of the present invention, 0.3 g of d-arrestrin was added and dissolved in 20 ml of acetone, and the carrier for mosquito coils (tab powder: kashiwa powder: wood powder in 4: 3: 3 ratio) After mixing uniformly with 99.4 g, add 120 ml of water and fill. The kneaded product is molded and dried to obtain each mosquito coil.

Formulation Example 10

Electric mosquito collection mat

Acetone is added to each of 0.4 g of each of the present compounds (1) to (41), 0.4 g of d-arrestrin and 4 g of vinylbutoxide, and dissolved to make 1 Oral in total. 0.5 ml of this solution was evenly impregnated into a 2.5 cm x 1.5 cm, 0.3 cm thick base for electric mat (a fibril of a mixture of cotton linter and pulp solidified in a plate shape), and Obtain an electric mosquito collection mat.

Formulation Example 11

Heating smoker

10 Omg of each of the compounds (1) to (41) of the present invention is dissolved in an appropriate amount of acetone, and impregnated in a porous ceramic plate having a thickness of 4. Ocm x 4. Ocm and a thickness of 1.2 cm. obtain.

Formulation Example 12

Bait

Each of the compounds (1) to (41) of the present invention is dissolved in 0.5 nil of 1 Omg of acetone, and this solution is mixed with animal solid feed powder (breeding and breeding solid feed powder CE-2, Nippon Clear Co., Ltd.). Process into 5g and mix evenly. The acetone is then air-dried to obtain 0.5% of each bait.

Next, Test Examples show that the compounds of the present invention are useful as active ingredients for insecticides and acaricides. The compounds of the present invention are represented by the above compound numbers, and the compounds used for comparison are represented by the compound symbols shown in Table 34. Table 3 4

Test example 1

(Insecticidal test on hamoso tow)

2 ml of a 200-fold diluted solution (500 ppm) of the test compound emulsion obtained in accordance with Formulation Example 1 in water was impregnated with 13 g of artificial feed for hamomyo tori prepared in a polyethylene roller having a diameter of 11 cm. Was. Among them, 10 larvae of the 4th-instar hammoshot were released, and after 6 the larvae were examined for their life and death, and the mortality was calculated (2 repetitions).

As a result, the compounds of the present invention (1) to (3), (8) to (: 11), (13) to (14), (17) to (18), (24), (27) to (32) (34) to (36) showed a mortality of 80% or more. In contrast, the mortality of compounds (A) and (B) used for the control

Test example 2

(Insecticidal test on Japanese moth)

To a 200-fold diluted solution of water (50 OPPID) of the test compound obtained according to Formulation Example 1 with water, add the spreading agent Linow (manufactured by Nippon Agrochemical Co., Ltd.) to a 1000-fold diluted concentration. This was applied to potted cabbage (5-leaf stage) at a rate of 25 ml per pot. After air-drying the plants, 10 of the 3rd instar larvae were released. 4 After that, he investigated the life and death and calculated the mortality.

As a result, the compounds (28), (31), (34), and (36) of the present invention each showed a mortality of 80% or more. In contrast, the mortality of the compounds (A) and (B) used as the control was 0%.

Test example 3

(Test for Nisenamihadani)

Seven days after sowing, 10 female adult females of two mosquitoes per leaf were infested with a potted beetle (primary leaf stage) at a temperature of 25 ° C. 6 After that, the emulsion of the test compound obtained according to Preparation Example 1 was diluted with water to the active ingredient at 50 ppm by spraying on a turntable and sprayed at 15 s: l per pot on a turntable. 2 ml of the same solution was poured into the soil and port. After that, we investigated the degree of damage of each plant by Hadani. The effect criterion is

1: There is hardly any damage.

÷: Some damage is observed.

++: Damage similar to the untreated area is observed.

And

The effects of the compounds of the present invention (20) and (24) were all judged to be one. On the other hand, the judgment effects of the compounds (A) and (B) used as the control were all.

As described above, the compounds of the present invention have excellent insecticidal and acaricidal efficacy.

Claims

The scope of the claims

1. General formula:

R ^l -ZY-OCH ₂ CH = CX ₂

[Wherein, R ¹ is an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a haloalkenyl group having 2 to 6 carbon atoms, and 3 to 9 carbon atoms. Represents an alkynyl group, a haloalkynyl group having 3 to 5 carbon atoms, an alkoxyalkyl group having 2 to 7 carbon atoms or an alkylthioalkyl group having 2 to 7 carbon atoms, or an alkyl group having 1 to 4 carbon atoms, It may be substituted by an alkoxy group having 1 to 3 carbon atoms or a haloalkoxy group having 1 to 3 carbon atoms, and represents a cycloalkyl group having 3 to 6 carbon atoms, or represents an alkyl group having 1 to 4 carbon atoms. May be substituted with L, a cycloalkylalkyl group having 4 to 9 carbon atoms, or may be substituted with an alkyl group having 1 to 4 carbon atoms L, a cycloalkenyl group having 5 to 6 carbon atoms, or a cycloalkenyl group having 1 to 4 carbon atoms Alkyl group It is either also represent good cycloalkenylalkyl group having a carbon number of 6 to 8, or an expression:

Q ₂ Q ₅

A--

RRCII

3 2 1

C¾ 2) no m.

Q ₇ (In the formula, A represents an optionally substituted phenyl group, an optionally substituted naphthyl group or an optionally substituted heterocyclic group,

B represents an oxygen atom, S (0) n group, NR ¹¹ group, C (= 〇) G group or a GC (= 〇) group (wherein, n represents an integer from 0 to 2, R ¹¹ is a hydrogen atom ' Or G represents an alkyl group having 1 to 3 carbon atoms, G represents an oxygen atom or an NR ¹⁵ group, and R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

RK R ³ , RR ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a trifluoromethyl group, and R ⁷ and R ⁸ each independently represent a hydrogen atom or a carbon number Represents an alkyl group, a trifluoromethyl group or a halogen atom of 1 to 3,

R ^{1 D} represents a hydrogen atom, a halogen atom or a methyl group, i represents an integer of 0 to 6, j represents an integer of 1 to 6, k represents an integer of 0 to 4, 1 represents 1 or Represents 2 and m represents an integer from 0 to 2. )

Represents Q, Q ₂ , Q ₃ , Q ₄ , Q ₅ , Q ₆ , Q-> Q ₈ or Q ₉ .

Z represents an oxygen Harachi, ^ sulfur atom or NR ¹² group (herein, R ¹² is was or hydrogen atom represents. Alkyl radicals of one to three carbon atoms). Y is the formula:

• A

'λ [people

oz; ero / s6dr / XDd

C60SI / 96 ΟΛλ (Wherein, R ¹³ is each independently a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, an alkyl group having 2 to 4 carbon atoms or a group having 2 to 4 carbon atoms. Represents a haloalkenyl group of 4, and p represents an integer of 0 to 3. In each of the structural formulas of Y! YS, the left bond of the two bonds is bonded to Z.) in indicated by _{_{_{Υ 2, Υ 3, Υ 4}}} , Υ 5, Υ 6, represent Upsilon ?, Upsilon ₈ or Upsilon _9.

X each independently represents a chlorine atom or a bromine atom. ] The dihalopropene compound shown by these.

2. Alpha Chikaraku (R ¹⁴⁾ Good Fuyuniru group or optionally substituted with q (R ¹⁴⁾ represent a naphthyl group which may be substituted with q, or an oxygen atom, a Iou atom or a nitrogen atom of at least 1 containing Ke, (R ¹⁴⁾ or be replaced with q representing an Yoi heterocyclic 6-membered ring group, or an oxygen atom, including both 1 pc less Iou atom or a nitrogen atom, it is substituted with (R ¹⁴⁾ q Represents a 5-membered heterocyclic group which may be

Where q is an integer from 0 to 7,

RH is a halogen atom, a cyano group, a nitro group, a (alkoxy having 1 to 4 carbon atoms) carbonyl group, an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, and a 1 to 7 carbon atoms Alkoxy group, haloalkoxy group having 1 to 3 carbon atoms, alkylthio group having 1 to 3 carbon atoms, haloalkylthio group having 1 to 3 carbon atoms, alkylsulfinyl group having 1 to 2 carbon atoms, alkylsulfonyl having 1 to 2 carbon atoms Group, haloalkylsulfinyl group having 1 to 2 carbon atoms, haloalkylsulfonyl group having 1 to 2 carbon atoms, alkenyloxy group having 3 to 6 carbon atoms, haloalkenyloxy group having 3 to 6 carbon atoms, 2 to 4 carbon atoms Alkenyl group, haloalkenyl group having 2 to 4 carbon atoms, alkynyl group having 2 to 4 carbon atoms, haloalkynyl group having 2 to 4 carbon atoms, alkynyloxy group having 3 to 6 carbon atoms Group, haloalkynyl O alkoxy group having 3 to 6 carbon atoms, carbon Alkoxyalkyl group of number 2 to 4, alkylthioalkyl group of coal number 2 to 4, amino group, dimethylamino group, acetate group, acetyl group, haloacetyl group, formyl group, carboxyl group, (carbon number 1 to 2 alkyl) aminocarbonyl, [di (alkyl having 1 to 2 carbons) amino] carbonyl, cycloalkyl having 3 to 6 carbons, cycloalkenyl having 5 to 6 carbons, carbon Represents a cycloalkyloxy group having 3 to 6 carbon atoms or a cycloalkenyloxy group having 5 to 6 carbon atoms, or a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, respectively. A phenyl group, a phenoquine group, a benzyl group or a phenyl group which may be substituted with an alkoxy group having 1 to 3 carbon atoms or a haloalkoxy group having 1 to 3 carbon atoms. The dihalide according to claim 1, wherein the dihaloxy group represents, or when d is 2 to 5, two adjacent R "are bonded to each other at the terminal to represent a trimethylene group, a tetramethylene group, a methylenedioxy group or an ethylenedioxy group. Mouth propene compounds.

3. The dihalopropene compound _{c according to} claim 2, wherein Y is Y,

4. The dihalopropene compound according to claim ₂ , wherein Y is Y2.

5. Y is dihalopropene compound according to claim 2, wherein a Y _3.

6. The dihalo proben compound according to claim 2, wherein Y is Y ₄ .

7. Y is dihalopropene compound according to claim 2 Ki戴is Y _5.

8. Upsilon is Upsilon ₆ claim 2 dihalopropene compound according.

9. Upsilon is dihalopropene compound according to claim 2 wherein the Upsilon _7.

1 0. Upsilon is dihalopropene compound according to claim 2 wherein the Upsilon _8.

1 1. Upsilon is Upsilon ₉ claim 2 dihalopropene compound according.

1 2. R ¹ is Q,, and, Alpha force (R ^{1 4)} Good phenylene group or optionally substituted with q (R ¹⁾ is substituted with q also be 2-pyridyl group wherein Item 3 The dihalopropene compound mentioned.

13. R ¹ is Q _2, and, A force (R ¹⁴⁾ q that is substituted may be phenylene Le group, (R ¹⁴⁾ may also be 2-pyridyl group or substituted with q (R ") 4. The dihalo proben compound according to claim 3, which is a 3-pyridyl group optionally substituted with q.

14. R ¹ is Q ₃ , and a phenyl group optionally substituted with A force (R ¹⁴ ) Q, a 2-pyridyl group optionally substituted with (R ″) q or (R ¹⁴ ) 4. The dihalopropene compound according to claim 3, which is a 3-pyridyl group optionally substituted with q.

15. R ¹ is Q ₄ , Q ₅ , Q ₆ , Q ₇ , Q ₈ or Q ₉ , and is a funinyl group optionally substituted with A force (R ¹⁴ ) q, substituted with (R ¹⁴ ) q 4. The dihalopropene compound according to claim 3, which is a 2-pyridyl group or a 3-pyridyl group optionally substituted with (R ¹⁴ ) q.

16. The dihalo proben compound according to claim 12, wherein Z is an oxygen atom, R ¹³ is a halogen atom, and p is 0 or 1.

17. Z is an oxygen atom, R ² , R ³ and R ⁴ are hydrogen atoms, i is an integer from 0 to 3, R ¹³ is a halogen atom, and 14. The dihalopropene compound according to claim 13, wherein p is 0 or 1.

18. Z is an oxygen atom, and, B is an oxygen atom, a C0 ₂ group or CO NH group, and a R ^2, R ³ and R ⁴ are hydrogen atoms, and i is 2 or 3 15. The dihalopropene compound according to claim 14, wherein R ¹³ is a halogen atom, and p is 0 or 1.

19. The compound according to claim 1, which is 2- (1-chloro-3--5- (trifluoromethyl) -1-pyridyloxy) -1-5- (3,3-dichloro-2-propenyloxy) naphthalene. Dihalopropene compounds.

20. The dihaloproben according to claim 1, which is 1- (3-bromo-5- (trifluoromethyl) -12-pyridyloxy) -12-chloro-5- (3,3-dichloro-2-propidinoloquine) naphtalene. Compound.

21. The dihalopropene compound according to claim 1, which is 1- (3,3-dichloro-2-proenyloxy) -1-5- (4- (4-1 (trifluoromethyl) phenyl) butyloxy) naphthalene.

22. The dihalopropene compound according to claim 1, which is 2-chloro-5- (3,3-dichloro-2-propenyloxy) -11- (4- (4- (trifluoromethyl) phenyl) butyloxy) naphthalene.

23. The dihalopropene compound according to claim 1, wherein the dihalopropene compound is 1- (3,3-dichloro-2-provenyloxy) -1-5- (3- (4- (trifluoromethoxy) funinoxy) propyroxy) naphthalene.

24. The compound according to claim 1, which is 2-chloro-1,5- (3,3-dichloro-2-propenyloxy) 1-1 (3- (4- (trifluoromethyl) benzoylamino) propyloxy) naphthalene.

25. An insecticide or acaricide characterized by containing the dihalopropene compound according to claim 1 as an active ingredient.

26. General formula:

[Wherein, Z and X represent the meaning described in claim 1, and Y _{1 ()} represents Υ], Υ ₂ , Υ _3, or in claim 1. ]

A compound represented by the formula:

27. The compound according to claim 26, wherein Y ₁₀ is Y.

28 Υ]. The compound of claim 26, wherein There is Upsilon _2.

29. The compound according to claim 26, wherein Υ _{1 ()} is Υ ₃ .

30. The compound according to claim 26, wherein Y _{1 ()} is Y ₄ .

31. The compound according to claim 27, wherein Ζ is an oxygen atom, R ¹³ is a halogen atom, and ρ is 0 or 1.

32. The compound according to claim 26, which is 5- (3,3-dichloro-2-propenyloxy) -11-naphthol.

33. The compound according to claim 26, which is 2-chloro-5- (3,3-diclo-1--2-provenyloxy) -11-naphthol.