WO2001068617A1

WO2001068617A1 - Carbamoyltetrazolinones and herbicides

Info

Publication number: WO2001068617A1
Application number: PCT/JP2001/002088
Authority: WO
Inventors: Masatoshi Ohnari; Koichi Nishio; Yasuhiro Sakurai; Katsushi Morimoto; Kunimitsu Nakahira; Nobuyuki Hamada; Tooru Ohki; Junko Noguchi; Shigeomi Watanabe
Original assignee: Nissan Chemical Industries, Ltd.
Priority date: 2000-03-16
Filing date: 2001-03-16
Publication date: 2001-09-20
Also published as: AU2001241167A1

Abstract

Carbamoyltetrazolinones of the following general formula (1); agricultural chemicals containing these compounds; and herbicides containing the same wherein L?1 is CR2R3; L2 is CR4R5, CR4R5CR6R7¿, or the like; at least one of R?1, R2, R3, R4, R5, R6 and R7¿ is phenyl (which may be substituted with C¿1-4? alkyl or the like) and the others are each independently hydrogen, C1-4 alkyl, or the like; and R?12 and R13¿ are each independently hydrogen, C¿1-6? alkyl, C3-6 cycloalkyl, or the like.

Description

Description Lumbamoyl tetrazolinones and herbicides Technical field

TECHNICAL FIELD The present invention relates to rubbamoylte trazolinones and pesticides containing them as an active ingredient, particularly herbicides.

Background art

Japanese Patent Application Laid-Open No. Sho 60-146, 679, Japanese Patent Application Laid-Open No. 62-12767, Japanese Patent Application Laid-Open No. Hei 6-30661, U.S. Pat. 2, U.S. Patent No. 503 075, European Patent No. 0 571 854, European Patent No. 0 571 855, Japanese Unexamined Patent Application Publication No. 8-81,559, Japanese Unexamined Patent Application Publication No. 9 9 7 5, European Patent Application 0 7 7 1 9 9 7, European Patent Application 0 9 0 2 0 2 8, Japanese Patent Application Laid-Open No. 8-1933 74, Japanese Patent Application Laid-Open No. 8-222 5 Kaihei 8-2595548 and Japanese Patent Application Laid-Open No. 11-180965 disclose that tetrazolinones have herbicidal activity.

An object of the present invention is to provide a pesticide, particularly a herbicide, having excellent potency, which comprises a potato rubamoyl tetrazolinone as an active ingredient.

As a result of intensive studies to solve the above problems, the inventors of the present invention have found that novel rubamoyl tetrazolinones have herbicidal activity and selectivity for crops, and have completed the present invention. Disclosure of the invention

That is, the present invention relates to the following formula 1)

In the formula, L ¹ represents C R2R ³ ;

L ² represents CR ⁴ R ⁵ , CR ⁴ R ⁵ CR ⁶ R ⁷ , CR ⁴ R ⁵ CR ⁶ R ⁷ CR ⁸ R ⁹ or CR RSC I ^ i C RSi C R'OR ¹¹ ,

^{^{R ', R 2, RR 4}} , R 5, R 6, R 7, R 8, RR 1. And at least one of R ¹ ′ is a phenyl group (provided that the phenyl group is a C ₄ -4 alkyl group, a Ci ₄ haloalkyl group, a ₄ alkoxy group, a cyano group, a nitro group, and a halogen group. . which by the one or more substituents the same or different selected from atoms connexion may be substituted), 5 heterocycle or a C ₃ to 6-membered - ₆ cycloalkyl group and the other is independently hydrogen atom, - ₄ alkyl group, a haloalkyl group, c, - ₄ alkoxy group, Shiano group, a two-Toro group or a halogen atom,

R ¹² and R ¹³ are each independently hydrogen atom, C, - ₆ alkyl group, C ₃ - _e a cycloalkyl group, C ₃ - ₆ cycloalkenyl group, C ₂ - ₄ alkenyl group, Ji ₂ - ₄ § Rukiniru group, - ₄ haloalkyl groups, C ₃ - ₆ 2 alkyl group substituted with a cycloalkyl group, - ₄ alkoxy group -, (wherein, R ¹² and R ¹³ are simultaneously C, never represents a ₄ alkoxy group.) C Bok ₄ alkoxy C, - ₄ alkyl group,

C ₄ alkylthio C, — ₄ alkyl group, phenyl group (provided that the phenyl group is C,

_ ₄ alkyl group, C, - ₄ haloalkyl group, an alkoxy group, Shiano group, may be substituted by the same or different and one or more location substituent selected from the two-Toro groups and halogen atoms. ), Benzyl group, pyridin-1-yl group (provided that R ¹² and R ¹³ do not simultaneously represent a pyridin-1-yl group), pyrrolidine-1- Yl group (however, R ^{12 and} R ¹³ do not simultaneously represent a pyrrolidine-11-yl group), morpholin-11-yl group (where R ¹² and R ¹³ are morpholin one 1 one I situations represent Le group les.) or 3, 6 dihydric mud represents an 2 H- pyran one 4-I group, provided that the nitrogen atom R ¹² and R ¹³ bound a monitor 3 rather it may also be configured to 9-membered ring, oxygen atom, a sulfur atom, C, - ₄ alkyl nitrogen atom which may be substituted with a group, a carbonyl group, a sulfonyl group or an unsaturated bond rather it may also be include Idei a ring C, - ₄ rather it may also be substituted by an alkyl group, the ring is d - crosslinking by ₄ alkylene Which may have been rather good, the ring by a benzene ring It may be condensed,

5- or 6-membered hetero ring is thiophene ring, furan ring, pyrrol ring, oxazole ring, thiazole ring, imidazole ring, isooxazole ring, isothiazole ring, pyrazole ring, 1,3,4-oxaziazo 1,3,4-thiadiazole ring, 1,3,4-triazole ring, 1,2,4-oxaziazol ring, 1,2,4-thiadiazol ring, 1,2 , 4-triazole ring, 1,2,3-oxaziazol ring, 1,2,3-thiadiazole ring, tetrazole ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, Represents a 1,3,5-triazine ring or a 1,2,4-triazine ring;

The present invention relates to a rubamoylte trazolinonone represented by the formula:, a pesticide containing the compound as an active ingredient, and a herbicide containing the compound as an active ingredient. BEST MODE FOR CARRYING OUT THE INVENTION

The substituents RR ² , R ³ , RR ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹ R ”, R ¹² and R ¹³ of the compound of the present invention and the synthetic intermediate of the compound of the present invention are specifically listed. However, the symbols have the following meanings, respectively.

Me: methyl group, Et: ethyl group, Pr—n: normal propyl group, Pr—iso: isopropyl group, Bu—n: normal butyl group, Bu—is 0: isobutyl group, Bu — Sec: secondary butyl group, Bu—ter: tertiary butyl group, Pen-n: normal pentyl group, Hex—n: normal hexyl group, Pr—eye: cyclopropyl group, Bu — Eye: cyclobutyl group, P en -cyc: cyclopentyl group, H ex— eye: cyclohexyl group, P h: phenyl group, P ip: piperidine 1-yl group, Pyrr: pyrrolidine 1 1-yl group, Morph: morpholin-1 1-yl group, Pyran: 3,6-dihydro-2H-pyran — 4-yl group, Pentene — eye: cyclopentene-1 1-yl group, Hexene— eye: cyclohexene 1-yl group

Equation (1)

, L ¹ is CR ² R ³ , L ² is CR ⁴ R ⁵ , CR ⁴ R ⁵ CR ⁶ R \ CR ⁴ R ⁵ CR ⁶ R ⁷ CR ⁸ R ⁹ or CR ⁴ R ⁵ CR ⁶ R ⁷ CR ⁸ R ⁹ C R'OR ¹¹ , R ', R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹ . As an example of R ¹¹ and R ¹¹ , when L ¹ -L ² is CR ² R ³ CR ⁴ R ⁵ , one or more of R ′, R ² , R ³ , R ⁴ and R ⁵ are: R ', RRRR ⁵ when the LL ² is ^{^{^{^{CR 2 R 3 CR 4 R 5}}}} CR 6 R 7, or any one of R ^e and R ^7, L ¹ - L ² is CR ² R ³ CR ⁴ R ⁵ CR ⁶ R ⁷ CR ^{8 For} R ⁹ , at least one of R ', RR ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R * and R ⁹ , L ^{1 and} L ² are CR ² R ³ CR ⁴ R ⁵ CR ⁶ R ⁷ CR ⁸ R ⁹ CR 'OR ¹¹ when RR ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , RR ¹ . And any one or Ph of ^{R 11, 2- CI- Ph, 3-} Cl-Ph, 4-Cl-Ph, 2, 4-Cl 2 -Ph, 3, 5-Cl 2 - Ph, 2, _{6-C1 2 -Ph, 2,} 3-Cl 2 - Ph, 2, 5-Cl 2 - Ph, 2-F-Ph, 3- F-Ph, 4-F- Ph, 2, 4-F 2 - Ph, 3, 5-F

₂ -Ph, 2-F-4-C1-Ph, 2-Br-Ph, 3-Br-Ph, 4-Br-Ph, 2-Me-Ph, 3-Me-Ph, 4-Me-Ph, _{2,4- Me 2 -Ph, 3, 5-} Me 2 -Ph, 2, 6-Me 2 - Ph, 2, 3- Me 2 -Ph, 2, 5-Me 2 - Ph, 2- MeO-Ph ,

3- MeO- Ph, 4-MeO- Ph , 2 - CF 3 -Ph, 3- CF 3 -Ph, 4- CF 3 -Ph, 2, 4, 6-Cl 3 -Ph, 2, 3, 5- C "- Ph, 2, 3 , 4-Cl 3 - Ph, 2-N0 2 -Ph, 3-N0 2 -Ph, 4-N0 2 -Ph, 2- CN- Ph, 3-CN- Ph, 4 -CN- Ph, 2-Cl-6-F-Ph, 2-EtO-Ph, 3-EtO-Ph ゝ 4-EtO-Ph, Pr-cyc, Bu-cyc, Pen-cyc, Hex-cyc, Thiophene 1-yl, 3-chlorothiophene 2-yl, 4-chlorothiophene 2-yl, 5-chlorothiophene 2-yl, 3,4-dichlorothiophene 2-yl , 3,5-Dichlorothiophene-2-yl, 4,5-Dichlorothiophene-2-yl, 3,4,5-Trichlorothiophene-2-yl, 3-Bromothiophene-2-yl 4-bromothiophen-2-yl, 5-bromothiophen-2-yl, thiophen-3-yl, 2-chlorothiophen-1-yl, 4-chlorothiophene-3-yl, 5-chlorothiophene-3-yl, 2,4-dichlorothiophene-3-yl, 2,5-dichlorothiophene-3-yl, 4,5-dichloro Thiophene-1-yl, 2,4,5-trichlorothiophene-3-yl, furan-2-yl, furan-3-yl, pyrroyl-11-yl, pyrrole 1-yl, pyrroyl 3-yl, oxazol 1-yl, oxazolo 4-yl, oxazole-5-yl, thiazole 1-2-yl, thiazole 1-4-1yl , Thiazole-5-yl, imidazole-1-yl, imidazo-1ru 2-yl, imidazo-1ru 41-yl, imidazo-1-5-yl, isoxoxazo-1-3ル, キサ一キサ 4 4 、、, ォォキサ 5 —, 5 イIsothiazole 4-yl, isothiazoyl 5-yl, pyrazole- 1-yl, pyrazoyl 3-yl, pyrazole 4-yl, pyrazoyl 5-yl, 1-methyl-3, 5- 4-chloro-1,4-methyl-5-chloropyrazole-4-yl, '1-methyl-5-chloro-3-3-trifluoromethylrubirazole-41-yl, 1,3,4-oxoxadiazo-2-yl 1,3,4-thiadiazol-2-yl, 1,3,4-triazole-11-yl, 1,3,4-triazole-2-yl, 1,2,4-oxaziaziol 3-yl, 1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol3 3-yl, 1,2,4-thiadiazol-5-yl, 1,2 , 4—triazo 1-yl, 1, 2, 4—triazole 3-yl, 1, 2, 4—triazo —Lou 5—yl, 1,2,3—oxaziaziruru 41—1,1,2,3—oxaziaziruru 5 1 ル 1,1,2,3—thiadiazole 3—yl, 1,, 2,3-Thiadiazole—5-yl, 1,2,3,4-tetrazol—11-yl, 1,2,3,4-tetrathrazole-5-yl, 1,2,3,5 —Tetrazo 1-yl, 1,2,3,5—Te torazol-41-yl, pyridine-12-yl, pyridin-13-yl, pyridin-4-yl, 2, 6-dichrolic pyridine 14-yl, pyrimidine 1-yl, pyrimidine 1-yl, pyrimidine 41-yl, pyrazine 1-2-yl, pyridazine 3- Yl, pyridazine 4-1yl, 1,3,5—triazine-1-2-yl, 1,2,4-triazine-1-3-yl, 1,2,4—triazine 5- And 1, 2, 4, 4-triazine-6-yl, etc. A substituent, other H, Me, Et, Pr-n, Pr-iso, Bu-n, Bu-iso, Bu- sec, Bu- ter, CH 2 F, CH 2 C1, CH 2 Br, CH 2 I, CHF 2, CHC1 2, CHBr 2, CF 3> CC1 3 _{_{, CBr 3, CC1F 2, CBrF}} 2, CH 2 FCH 2, CHF 2 CH 2, CF 3 CH 2, CF 3 CF 2, CF3CF2CF2 C ICH2CH2> BrCH2CH2, CC 13CH2> CFsCH2CH2, CC 13CH2CH2 C1CH2CH 2 CH2, FCH 2 CH ₂ CH ₂ , CF ₃ CF ₂ CH ₂ , C1CH ₂ CH ₂ CH ₂ CH ₂ , OMe, OEt, OPr-n, OPr-iso, OBu-n, OBu-iso, OBu-sec, OButer, CN, N0 _2, F, is a substituent selected from C and Br and I and the like. Preferred combinations of these substituents include, for example, when L ¹ -L ² is CR ² R ³ CR ⁴ R ^S , one of RR ² , R ³ , R ⁴ and R ⁵ is L ¹ — When L ² is CR ² R ³ CR ⁴ R ⁵ CR ⁶ R ⁷ , one of R ′, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ is L ¹ - when L ² is ^{^{^{^{CR 2 R 3 CR 4 R 5}}}} CR 6 R 7 CR 8 R 9 R ', the ^{^{^{R 2, R 3, R 4}}} , R 5, R 6, R 7, R 8 and R ⁹ If one of them is L ¹ — L ² is CR ² R ³ CR ⁴ R ⁵ CR ⁶ R ⁷ CR ⁸ R ⁹ C R'OR ¹¹ , R ', RR ³ , RR ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are Ph, 2-Ct Ph, 3-Cl-Ph, 4-Cl-Ph, 2,4-Cl ₂ -Ph, 3, 5 -Cl ₂ -Ph, 2, 6-Cl ₂ -Ph, 2, 3-Cl ₂ -Ph, 2, 5-Cl ₂ -Ph, 2-F- Ph, 3-F-Ph, 4-F- Ph _{, 2, 4 - F 2 -} Ph, 3, 5-F 2 - Ph, 2 - F-4-Cl-Ph, 2-B r-Ph, 3-Br- Ph, 4- Br- Ph, 2- Me-Ph ゝ 3-Me- Ph, 4-Me- Ph, _{2, 4-Me 2 -Ph,} 3, 5-Me 2 - Ph, 2, 6-Me 2 - Ph, 2, 3 - Me 2 - Ph, 2, 5- Me 2 -Ph, 2-MeO-Ph , 3-MeO- Ph, 4- MeO- Ph, 2 -CF 3 -Ph, 3-CF 3 -Ph, 4- CF 3 -Ph, 2, 4, 6-Cl 3 -Ph, 2, 3, 5 _{-Cl 3 - Ph, 2, 3} , 4- Cl 3 -P h, 2- N0 2 - Ph, 3-N0 2 -Ph, 4-N0 2 -Ph, 2_CN-Ph, 3-CN-Ph, 4 -CN- Ph, 2-CI-6-F-Ph,

2-EtO-Ph, 3-EtO-Ph and 4-EtO-Ph are substituents selected from the group consisting of H, Me, F and CI. is then, for example, L ¹ one L ² is CH ₂ - CH ₂ in which R ¹ is Ph, 2- Cl-Ph, 3 -C1- Ph, 4-Cl-Ph, 2, 4-Cl 2 -Ph, 3 _{, 5- Cl 2 - Ph, 2} , 6- Cl 2 - Ph, 2, 3-Cl 2 - Ph, 2, 5-Cl 2 - Ph, 2- F-Ph, 3-F-Ph, 4-F _{-Ph, 2, 4-F 2} - Ph, 3, 5 - F 2 - Ph, 2_F- 4- CI- Ph, 2- Br-Ph, 3-Br-Ph, 4 - Br- Ph, 2 - Me -Ph ゝ

3- Me - Ph, 4- Me- Ph, 2, 4- Me 2 -Ph, 3, 5- Me 2 - Ph, 2, 6-Me 2 -Ph, 2, 3- Me 2 -Ph, 2, 5-Me ₂ -Ph, 2-MeO-Ph, 3-MeO-Ph, 4-MeO-Ph, 2-CF ₃ -Ph, 3-CF ₃ -Ph, 4-CF ₃ -Ph, 2, 4,

_{6- Cl 3 -Ph, 2, 3} , 5- Cl 3 - Ph, 2, 3, 4-Cl 3 -Ph, 2- N0 2 - Ph, 3-N0 2 -Ph, 4-N0 2 - Ph, 2-substitution selected from CN-Ph, 3-CN-Ph, 4-CN-Ph, 2-CI-6-F-Ph, 2-EtO-Ph, 3-EtO-Ph and 4-EtO-Ph Combinations that are groups are mentioned.

Specific examples of the substituents R ¹² and R ¹³ include H, Me, Et, Pr-n, Pr-iso, Bu-n, Bu-iso, Bu - sec, Bu - ter, CHMeCHMe 2, Pen - n, Hex - n, Pr - cyc, Bu - cyc, Pen - cyc, Hex - cyc, CH 2 Pr- cyc, CH 2 Bu-cyc, CH 2 Pen -cyc, CH ₂ Hex-cyc CH ₂ CH ₂ Pr-cyc, CH ₂ CH = CH ₂ , CH ₂ CH = CHMe, CH ₂ CMe = CH ₂ , CH ₂ CH ₂ CH = CH ₂ , CH ₂ C , CH ₂ C three _{CMe, CHMeC≡CH, CMe 2 C≡ CH} , CH 2 OMe, CH 2 OEt, CH 2 0Pr- n, CH 2 OBu- n, CH 2 0Bu- iso, CH 2 0Bu-sec, CH _{_{2 0Bu-ter, CH 2 CH}} 2 0Me, CH 2 CH 2 0Et, CH 2 CH 2 OPr- n, CH 2 CH 2 CH 2 OMe, CH 2 CH 2 CH 2 OEt, CH 2 CH 2 CH 2 CH 2 OMe , CH ₂ SMe, CH ₂ SEt, CH ₂ SPr-n, CH ₂ SPr-iso, CH ₂ SBu-n, CH ₂ SBu-iso, CH ₂ SBu-sec, CH ₂ SBu-ten CH ₂ CH ₂ SMe, _{_{_{CH 2 CH 2 SEt, CH 2}}} CH 2 SPr-n, CH 2 CH 2 SPr-iso, CH 2 CH 2 SBu- n, CH 2 CH 2 SBu-iso, CH 2 CH 2 SBu- sec, CH 2 CH 2 SButer, CH ₂ CH ₂ CH ₂ SMe, CH ₂ CH ₂ CH ₂ SEt, CH ₂ CH ₂ CH ₂ SPr-n, CH ₂ CH ₂ CH ₂ SPr-iso, CH ₂ CH ₂ CH ₂ SBu-n, CH ₂ CH ₂ CH ₂ SBu- iso, CH ₂ CH ₂ CH ₂ SBu- sec, CH ₂ CH ₂ CH ₂ SButer, CH ₂ CH ₂ C1, CH ₂ CH ₂ C1, CH ₂ CH ₂ Br, CH ₂ CF ₃ , CH ₂ CC1 = CH ₂ , Ph, 2-Cl-Ph, 3_C Bok Ph, 4- Cl_Ph, 2, 4 -Cl 2 - Ph, 3, 5- Cl 2 -Ph, 2, 6- Cl 2 -Ph, 2, 3-Cl 2 - Ph, 2, 5- Cl 2 _Ph, 2-F- Ph, 3 -F-Ph, 4 - F-Ph, 2, 4 - F 2 -Ph, 3, 5-F 2 - Ph, 2- F-4- CI- Ph, 2 - Br-Ph, 3_Br- Ph, 4 - Br-Ph, 2-Me-Ph, 3- Me- Ph, 4-Me-Ph, 2, 4- Me 2 -Ph, 3, 5-Me 2 - Ph, 2, 6-Me ₂ -Ph, 2, 3-Me ₂ -Ph, 2,5-Me ₂ -Ph ゝ 2-MeO-Ph, 3-MeO-Ph, 4-MeO-Ph, 2-CF _3- _{Ph, 3- CF 3 - Ph,} 4- CF 3 -Ph, 2, 4, 6-Cl 3 - Ph, 2, 3, 5-Cl 3 -Ph, 2, 3, 4-Cl 3 - Ph, 2 _{-N0 2 - Ph, 3 - N0} 2 _Ph, 4_N0 2 -Ph, 2-CN- Ph, 3-CN- Ph, 4- CN- Ph, CH 2 Ph, OMe, OEt, OPr- n, OPr-iso , OBu-n, OBu-iso, OBu-sec, OBu-ter, Pip, Pyrr, MorPh, Pyran> pentene-cyc and hexene-cyc ₀

Specific examples for configuring 3-9 membered ring together with the nitrogen atom to which substituent R ¹² Oyopi R ¹³ are attached, the following structures are exemplified.

880Z0 / T0dT / X3d .1989 / 10

Among them, a particularly preferred combination of R ¹² and R ¹³ depends on the type of L′—L ^2. For example, R ¹² is an alkyl group having 1 to 4 carbon atoms and R ¹³ is Ph, 2- CI- Ph, 3- CI - Ph, 4-Cl-Ph, 2, 4-Cl 2 - Ph, 3, 5- Cl 2 -Ph, 2, 6 - Cl 2 - Ph, 2, 3- Cl 2 - _{Ph, 2, 5 - Cl 2} - Ph, 2- F_Ph, 3_F- Ph, 4- F_Ph, 2, 4-F 2 - Ph, 3, 5- F 2 - Ph, 2- F-4-C1- Ph , 2-Br- Ph, 3- Br-Ph, 4- Br-Ph, 2- Me-Ph, 3- Me- Ph, 4-Me- Ph, 2, 4-Me 2 -Ph, 3, 5- Me ₂ -Ph, 2, _{6-Me 2 - Ph, 2} , 3- Me 2 -Ph, 2, 5- Me 2 - Ph, 2-MeO - Ph, 3-MeO-Ph, 4-MeO-Ph, 2-CF 3 - P h _{, 3-CF 3 -Ph, 4} -CF 3 -Ph, 2, 4, 6-Cl 3 - Ph, 2, 3, 5-Cl 3 -Ph, 2, 3, 4- Cl 3 - Ph, 2- _{N 0 2 - Ph, 3-} N0 2 - Ph, 4 - N0 2 -Ph, 2-CN-Ph, 3- CN- Ph, 4- CN-Ph, 2 - CI- 6-F-Ph, 2- Combinations which are substituents selected from EtO-Ph, 3_EtO-Ph and 4-EtO-Ph can be mentioned. The compound (1) R of the present invention may have 1, N optical isomers, and all such optical isomers are included in the present invention. Λ-Ο

/

The compound (1) of the present invention can be easily produced by the following Reaction Scheme 1.

(Reaction formula 1)

No

(3)

(1)

(2)

In the formula, L ¹ LRR ¹² and R ¹³ represent the same meaning as described above, and Z represents a halogen atom.

Reaction formula 1 shows a method for producing the compound (1) of the present invention by reacting a tetrazolinone (2) with a carbamoyl halide (3) in the presence or absence of a base.

(3) is usually used in a molar amount of 1 to 10 times, preferably 1 to 2 times the molar amount of (2).

Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate and sodium hydride, pyridine, 4-dimethylaminopyridine, triethylamine, N, N_dimethylaniline And organic bases such as 1,8-diazabicyclo (5.4.0) —7-indene (DBU); organic lithiums such as n-butyllithium and sec-butyllithium; and organic lithium amines such as lithium diisopropylamide. Dos. The base is used usually in an amount of 0 to 10 moles, preferably 1 to 2 moles, relative to (2).

This reaction proceeds even without solvent, but a solvent can be used if necessary. Solvent reacts There is no particular limitation as long as it is inert to water, but, for example, aliphatic or aromatic hydrocarbons such as hexane, cyclohexane, benzene and toluene, carbon tetrachloride, chloroform and 1,2-dichloroethane Halogenated hydrocarbons such as ethylene, ethers such as Jethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methylethyl ketone and methyl isobutyl ketone, and acetone. Nitriles such as tonitrile and propionitol; acid amides such as N, N-dimethylformamide and N, N-dimethylacetamide; sulfur-containing polar solvents such as sulfolane; Phosphorus-containing polar solvents such as hexamethylphosphoramide, and organic bases such as pyridine.

The reaction temperature is usually from 90 to 200 ° C, preferably from 0 to 120 ° C.

The reaction time is generally 0.05 to 100 hours, preferably 0.5 to 10 hours. Hereinafter, synthesis examples of the compound of the present invention will be specifically described with reference to Examples and Reference Examples, but the present invention is not limited thereto.

Example

(Example 1)

Synthesis of 1- (1-phenylcyclopropyl) -14_ (N-phenyl-1-N-isopropylcarbamoyl) -15 (4H) -tetrazolinone (Compound No. 1 of the present invention)

Toluene (8 ml) in 1- (1-phenylcyclopropyl) 1-5 (4H) -tetrazolinone (0.20 g, 0.99 mm 01)> 4-dimethylaminopyridine (0.1 6 g, 1.3 mm 01) and N-phenyl-N-isopropyl-potassium rubamoyl chloride (0.20 g, 1.0 mm 01) were added, and the mixture was refluxed for 3 hours. After cooling to room temperature, a saturated aqueous solution of sodium hydrogen carbonate was added, and the mixture was extracted with ethyl acetate. The obtained ethyl acetate solution was washed successively with water, 5% hydrochloric acid, and a saturated aqueous solution of sodium chloride. The residue obtained by drying over anhydrous sodium sulfate and evaporating the solvent was washed with diisopropyl ether and dried to obtain 0.27 g of the desired product. Mp 125-126.

(Example 2)

1 — (1-(3-Fluorophenyl) cyclobutene pill) 1-4-(N-phenyl-1-N-isopropyl-rubamoyl) 1-5 (4 H)-tetrazolinone (Compound N of the present invention 0.3 2) Synthesis of

1— (1— (3-fluorophenyl) cyclopropyl pill) in acetonitrile (10 ml) —5 (4H) —tetrazolinonone (0.50 g, 2.3 mm 01) Then, anhydrous calcium carbonate (0.47 g, 3.4 mm 01) and N-phenyl-N-isopropylcarbamoyl chloride (0.45 g, 2.3 mmo 1) were added, and 6 Returned for 5 hours. After cooling to room temperature, a saturated aqueous solution of sodium hydrogen carbonate was added, and the mixture was extracted with ethyl acetate. The obtained ethyl acetate solution was sequentially washed with water, 5% hydrochloric acid and a saturated aqueous solution of sodium chloride, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain 0.87 g of the desired product. 933-94 ° C.

Reference example

(Reference example 1)

Synthesis of 1- (1-phenylcyclopropyl) -5 (4H) -tetrazolinone

Trimethylsilyl azide (2.30 g, 20.0 mm 01) was added at 90 ° C to 1-phenylcyclopropanecarboxylic acid chloride (3.00 g, 16.6 g). mm 0 1) Was added dropwise over 0.5 hour, and the mixture was further refluxed for 1 hour. After cooling to room temperature, the boron trifluoride getyl ether complex (0,000) dissolved in trimethylsilyl azide (2.80 g, 25.0 mm 01) and 1,2-dichloroethane (25 ml) was used. 23 g, 1.6 mmo 1) were added and refluxed for 1.5 hours. After cooling to room temperature, the mixture was poured into ice water (200 m 1) and extracted with Kuguchiguchi Holm. The organic layer was dried over anhydrous sodium sulfate, and the residue obtained by evaporating the solvent was dissolved in ethyl acetate (100 ml). A saturated aqueous solution of sodium hydrogen carbonate was added, and the mixture was extracted again. The resulting aqueous layer was adjusted to pH 1 by adding 35% hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed sequentially with water and a saturated aqueous solution of sodium chloride, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain 2.0 g of the desired product. Melting point 1 2 4 — 1 2 6.

(Reference example 2)

Trans-1- (2-phenylphenylpropyl) -5 (4H) -tetrazolinone

The synthesis was carried out in the same manner as in Reference Example 1 using trans-2-phenylphenylpropanecarboxylic acid chloride as a starting material. With a melting point of 1 2 8—1 3 0.

(Reference example 3)

1— (1— (4-Crophenyl) cyclopropyl) 1-5 (4H) -te Synthesis of trazolinone

Synthesized in the same manner as in Reference Example 1 using 1- (4-chlorophenyl) 1-cyclopropanecarboxylic acid chloride as the starting material, (Reference example 4)

Synthesis of 1- (1-phenylcyclobutyl) -5 (4H) -tetrazolinone

The synthesis was carried out in the same manner as in Reference Example 1 using 1-phenylcyclobutanecarboxylic acid as a raw material. With a melting point of 6 8—70.

(Reference example 5)

Synthesis of 1- (1- (4-chlorophenyl) cyclobutyl) -5 (4H) -tetrazolinone

The synthesis was carried out in the same manner as in Reference Example 1 using 1- (4-chlorophenyl) cyclobutanecarboxylic acid chloride as the starting material. Melting point 15 5—1 59. C.

(Reference example 6)

(1) Synthesis of 1- (3-fluorophenyl) cyclopropane isocyanate

To a solution of sodium azide (4.82 g, 74.2 mm 01) in water (20 ml) at 5 ° C was added 1- (3-fluorophenyl) cyclopropanecarboxylic acid chloride (7 A solution of 38 g (37. 1 mmol) in acetone (60 ml) was added dropwise. After stirring at room temperature for 0.5 hour, toluene (55 ml) was added for extraction. The toluene layer was washed sequentially with water and a saturated aqueous solution of sodium chloride, and then dried over anhydrous magnesium sulfate. Profit The obtained toluene solution of 1- (3-fluorophenyl) cyclopropanecarboxylic acid azide was added dropwise to a flask heated in a 120 oil bath. Generation of nitrogen gas was observed simultaneously with the dropwise addition. After the addition was completed, the mixture was refluxed for 0.5 hour, and the solvent was distilled off. The obtained residue was distilled under reduced pressure to obtain 5.90 g of the desired product. Boiling point 8 4— 8 5 ° CZ 0.2 mm H go

(2) Synthesis of 1— (1— (3-fluorophenyl) cyclopropyl) -5 (4H) -tetrazolinone

Sodium azide (0.60 g, 9.23 mm 01) and anhydrous aluminum chloride (0.06 g, 0.4) were added to N, N-dimethylformamide (5.0 ml). 5 mmo1) was added, and the mixture was stirred at 70 ° C for 10 minutes. One (3-fluorophenyl) cyclopropane isocyanate (1.60 g, 8.99 mm 01) was added, and the mixture was stirred at 90 ° C. for 4 hours. After cooling to room temperature, the mixture was poured into water (40 ml), adjusted to pH 1 by adding 35% hydrochloric acid, and extracted with getyl ether (100 ml). To the obtained organic layer was added a 1N aqueous solution of sodium hydroxide (100 ml), and the mixture was extracted again. The obtained aqueous layer was adjusted to pH 1 by adding 35% hydrochloric acid, and then extracted with getyl ether. The organic layer was washed successively with water and a saturated aqueous solution of sodium chloride, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain 1.75 g of the desired product. With a melting point of 1 17—1 18 Tables 1 and 2 show the structural formulas and proton NMR measurement results of the compounds synthesized by using the same method as in the above Examples and Reference Examples, together with the compounds of the above Examples.

However, the symbols in the table have the same meaning as described above. Table 1

^No. R ¹ L ¹ L ² NR ¹² R ¹³ Physical properties (melting point,)

1 ω

Ph CH ₂ CH -N (Pr-iso) Ph 9

2 Ph CH ₂ CH -NEt (Hex-cyc) i

Ph CH ₂ CH 1 9 1 — 1 0 * j

ο

4 H PhCH CH -N (Pr-iso) >> Ph reason: ^ Mr. H PhCH CH 'Y; Η ^ 4¾ 暂

H PhCH CH -N (Pr-iso) (2,4-F ₂ -Ph) oil im 1 *

7 4 -Cl-Ph CH ₂ CH: -N (Pr-iso) Ph

4 -Cl-Ph CH ₂ CH: CH2 -N (Pr-iso) Ph: 1 Female clam

9 4 -Cl-Ph CH ₂ CH: CH ₂ -NEt (Hex-cyc) Oil 晳

1 o Ph CH ₂ CHi -N (Pr-iso) (4-F-Ph) 94-9 6

1 1 Ph CH ₂ CH: -N (Pr-iso) (2- Me-Ph) Oil 晳

1 2 Ph CH ₂ CH: CH ₂ -N (Pr-iso) Ph

1 3 Ph CH ₂ CH2CH2 -NEt (Hex-cyc) Oil

1 4 Ph CH ₂ CH:-N (Pr-iso) (2- F- Ph) 103-1 0 4

1 5 Ph CH ₂ CH; -N (Pr-iso) (3-F-Ph) Oil

1 6 Ph CH ₂ CH: Roquinoline-1-yl oily substance

1 7 Ph CH ₂ CH _{: To} 2-methylpi. Ricin 1-yl oily substance

1 8 4EtO-Ph CH ₂ CH: 1 08-1 0 9

1 9 2 -Cl-Ph CH ₂ CH ₂ -N (Pr-iso) Ph Oil

2 0 2- -Cl-Ph CH ₂ CH ₂ -NEt (Hex-cyc) Oil

2 1 Ph CC1 ₂ CH ₂ -N (Pr-iso) Ph 1 2 2-1 2 3

2 2 Ph CC1 ₂ CH ₂ oil

2 3 2- -Me-Ph CH ₂ CH ₂ -N (Pr-iso) Ph Oil

2 4 2- -Me-Ph CH ₂ CH ₂ -N (Pr-iso) (4-F-Ph) Oil

2 5 2- -Me-Ph CH ₂ CH ₂ -NEt (Hex-cyc) Oil

2 6 Ph CH ₂ CH ₂ -NEt (CH ₂ CMe = CH ₂ ) Oil

2 7 2- -F-Ph CH ₂ CH ₂ -N (Pr-iso) Ph Oil

2 8 2- -F-Ph CH ₂ CH ₂ Oil

2 9 2- -F-Ph CH ₂ CH ₂ -N (Pr-iso) (2,4-F ₂ -Ph) Oil

3 0 Ph CC "CH ₂ -N (Pr-iso) (2,4-F ₂ -Ph) Oil

3 1 Ph CH ₂ CH ₂ -N (Pr-iso) (Hex-eye) Oil

3 2 3- -F-Ph CH ₂ CH ₂ -N (Pr-iso) Ph Oil

3 3 3- -F-Ph CH ₂ CH ₂ -N (Pr-iso) (4-F-Ph) Oil Table 1 (continued)

N 0 .R ¹ L ¹ L ² NR ^{1 2} R ¹³ Physical properties (melting point, ° C)

3 4 3-F-Ph CH ₂ CH ₂ Oil

3 5 Ph CC1 ₂ CH ₂ -N (Pr-iso) (4-F-Ph) Resinous substance

3 6 3-Me-Ph CH ₂ CH ₂ -N (Pr-iso) Ph Oil

3 7 3-Cl-Ph CH ₂ CH ₂ 1 1 5-1 1 6

3 8 3-Cl-Ph CH ₂ CH ₂ -N (Pr-iso) (4-F-Ph) 9 2-9 3

3 9 3-Cl-Ph CH ₂ CH ₂ -NEt (Hex-cyc) Oil

4 0 2-F-Ph CH ₂ CH ₂ -N (Pr-iso) (4-F-Ph) Oil

4 1 2-F-Ph CH ₂ CH ₂ -NEt (CH ₂ CMe = CH ₂ ) Oil

4 2 2-F-Ph CH ₂ CH ₂ -N (Pr-iso) (2-F-Ph) Oil

4 3 2-F-Ph CH ₂ CH ₂ -N (Pr-iso) (3-F-Ph) Oil

4 4 4-F-Ph CH 2 CH 2 • a- 1 2 7 - 1 2 9

4 5 4-F-Ph CH ₂ CH ₂ -NfPr-i¾o (4— F— Ph) 1 2 1-1 2 2

4 6 4-F-Ph CH ₂ CH ₂ -NEt (Hex o

o o-cyc) Oily substance

4 7 4-Me-Ph CH ₂ CH ₂ -N (Pr-iso) Ph 9 2-9 4

4 8 4-Me-Ph CH ₂ CH ₂ -N (Pr-iso) (4-F-Ph) Oil

4 9 4-Me-Ph CH ₂ CH ₂ -NEt (Hex-cyc) Oil

5 0 Chi-Shen Fen-2-yl CH ₂ CH ₂ -N (Pr-iso) Ph Oil

5 1-year-old phen-2-yl CH ₂ CH ₂ -N (Pr-iso) (4-F-Ph) 1 1 3-1 1 4

5 2 Chi-Shen Fen- _2- yl CH ₂ CH ₂ -NEt (Hex-cyc) Oil

5 3 Ph CH ₂ CH ₂ -N (Pr-iso) (cyclohexene-1-yl) Oil

5 4 Ph CH ₂ CH ₂ -N (Pr-iso) (4-Cl-Ph) 1 3 2-1 3 3

5 5 3-F-Ph CH ₂ CH ₂ -N (Pr-iso) (4-Cl-Ph) 7 1-7 2

5 6 3-F-Ph CH ₂ CH ₂ -N (Pr-iso) (2-F-Ph) Oil

5 7 3-F-Ph CH ₂ CH ₂ -N (Pr-iso) (3-F-Ph) 6 1-6 3

5 8 3-F-Ph CH ₂ CH ₂ -N (Pr-iso) (2-Me-Ph) Oil

5 9 3-F-Ph CH ₂ CH ₂ -N (Pr-iso) Oil

6 0 3-F-Ph CH ₂ CH ₂ Te'hydrohydroquinoline-1-yl Oil

6 1 3-F-Ph CH ₂ CH ₂ 2-Methyl ar. What. Rishi * -1-yl oily substance

6 2 3-F-Ph CH ₂ CH ₂ -NEt (CH ₂ CMe = CH ₂ ) Oil

6 3 CH-CH3 CH ₂ CH ₂ -N (Pr-iso) Ph 0 8-1 0 9

6 4 Thiophene-2-yl CH ₂ CH ₂ -N (Pr-iso) (4-F-Ph) 9 9-1 0 0

6 5 Ph CH ₂ CH ₂ -NEt (Morph) 1 2 8-1 2 9

6 6 Pr-cyc CH ₂ CH ₂ -N (Pr-iso) Ph Oil

6 7 3-F-Ph CH ₂ CH ₂ -N (Pr-iso) (2,4-F ₂ -Ph) 6 4-6 5

6 8 3-F-Ph CH ₂ CH ₂ -NEt (Morph) 1 2 3-1 2 4

6 9 Pen-eye CH ₂ CH ₂ 7 9-8 0

7 0 2-C1- 6-F- Ph CH ₂ CH ₂ -N (Pr-iso) Ph Oil

7 1 2-Cl-6-F-Ph CH ₂ CH ₂ -N (Pr-iso) (4-F-Ph) Oil

7 2 2,4-Cl ₂ -Ph CH ₂ CH ₂ -N (Pr-iso) Ph Oil

7 3 2,4- Cl ₂ -Ph CH ₂ CH ₂ -N (Pr-iso) (4-F-Ph) Oil

7 4 Ph CH ₂ CH ₂ -N (Pr-iso) (3-Me-Ph) Oil

7 5 Ph CH ₂ CH ₂ -N (Pr-iso) (4-Me-Ph) 8 9-9 0

7 6 Ph CH ₂ CH ₂ -N (Pr-iso) (2-Me0-Ph) Oil Table 1 (continued)

^No. R ¹ L ¹ L ² — NR ¹² R ' ³ Physical properties (melting point, ° C)

7 7 Ph CH ₂ CH ₂ -N (Pr-iso) (4- MeO- Ph) 8 0-8 3

7 8 Ph CH ₂ CH ₂ -NEtPh 6 9-7 0

7 9 Ph CH ₂ CH ₂ 1 1 2 1 1 1 3

8 0 Ph CH ₂ CH ₂ -N (Pr-iso) (Pyran) 9 2-9 5

Table 2

N o HNMR (solvent δ (p p m)

o

1 CDC1 ₃ 1.24 (d, J = 6.9Hz, 6H), 1.38 (s ,, 4H),

4.48-5.08 (m, IH), 6.70-7.2 (m, 10H)

o.

2 CDC 0.86-2.10 (m, 17H), 2.90- 3.80 (m, IH),

3.35 (q, J = 7.2Hz, 2H), 7.10-7.50 (m, 5H)

3 CDCU 1.30 (d, J = 6.8Hz, 6H), 1.55 (s, 4H),

4.48-5.03 (m, IH), 6.57-7.65 (m, 8H)

4 CDCU 0.97- 1.74 (m, 2H), 1.30 (d, J = 6.9Hz, 6H),

2.20-2.61 (m, IH), 2.94-3.35 (m, IH),

4.48- 5.08 (m, IH), 6.98- 7.57 (m, 10H)

5 CDCU 0.92-2.24 (m, 15H), 2.48- 2.94 (m, IH),

3.18-4.18 (m, 4H), 7.25 (s, 5H)

6 CDC 0.97-1.92 (m, 2H), 1.25 (d, J = 6.9Hz, 6H),

2.27- 2.70 (m, IH), 3.01- 3.40 (m, IH),

4.42-5.03 (m, IH), 6.61-7.59 (m, 8H)

7 CDCh 1.25 (d, J = 6.9Hz, 6H), 1.43 (s, 4H),

4.48- 5.03 (m, IH), 6.68-7.51 (m ₍ 9H)

8 CDCU 1.25 (d, J = 6.9Hz, 6H), 1.55-2.20 (m, 2H),

2.33-3.14 (m, 4H), 4.42- 4.99 (m, IH), 6.81- 7.40 (m, 9H)

9 CDCU 0.50- 2.46 (m, 15H), 2.46-3.87 (m, 7H), 7.35 (s, 4H) 10 CDCh 1.24 (d, J = 6.6Hz, 6H), 1.44 (s, 4H),

4.51-5.14 (m, 1H), 6.74-7.66 (m, 9H)

1 1 CDC "1.20 (d, J = 6.6Hz, 3H), 1.43 (s, .4H),

1.48 (d, J = 6.6Hz, 3H), 2.29 (s, 3H),

4.18-4.78 (m, IH), 6.66-7.44 (m, 9H)

1 2 CDCU 1.25 (d, J = 6.9Hz, 6H), 1.55-2.20 (m, 2H),

2.40-3.20 (m, 4H), 4.50-5.00 (m, IH), 6.90-7.40 (m, 10H)

1 3 CDC1 ₃ 0.50-2.40 (m, 15H), 2.45- 3.80 (m, 7H), 7.00-7.50 (m, 5H)

14 CDC "1.27 (d, J = 7.8Hz, 6H), 1.44 (s, 4H), 4.42-5.00 (m, IH),

6.77- 7.64 (m, 9H) (Η6 'ω) 86 · -9' (Ηΐ '^) Ζ \ ^ -OW

'' ιοαο 9 ε

'(Ηΐ' ω) 08 · ε-06 '(ΗΖΐ' ω) Ζ £-£ 9 · 0ιοαο ν ε

(Η8 '^) 9VL- V9

(HI '∞) ZO'S- OS' (Η 's) H' (Η9 ^<Z H9 '9 = Γ' P · ΐ ιααα ε ε

9 '-8 £ ^, 9 ο

'(Ηΐ'n>)S0'S-8f'(Η' s) 9 I '(Η9

'Ρ) Α2-ΐ ιοαο ζ ε

(HS 's) S £' Z '(Ηΐ' «ι) 66 · ε- 9 · £ '(Ηΐ'« 09-06

'(Η' m) 0f2-S '0' (Η9 'ζ Α = Γ' Ρ) ΐΐιοαο ΐ ε

(Η8 '^) LfL-ZV9' (HI '^) Z0 ^ -L £ ^

'(HZ' «S8 m '(Η9' ΖΗ9 · 9 = Γ 'Ρ) 9Ζ · ΐιοαο ο ε

(HA 'ω) ΐ8 ・ Ζ-9' O ^ -LZ ^

'(m' s) 0S'I '(Η9

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'(HI' ™) 08 · ε-06 '(ΗΑΐ' ∞) S £-IS ιοαο 8 ζ

(H6 'ID) 6S' A-V9 '(Ηΐ' ω) 66 ・ .οε '(H' s) 6 £ 'I' (Η9 'ZH8 ιοαο ί ζ

(HS's) ££-sjq) 88

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(H) 88 · Α— '(HZ' zHS "A = f 'b) SS'S 9Ζ

'(HI' ∞) 08ε-εΐ ・ ε '(Ηε' s) ss' (HST 06'O ιοαο s τ

0'S- Sfr

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S'I- 00 · ΐ ιοαο ε ζ οζ 8 · ε- Οΐ £

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(Hya '») Z, 0'8-88'9' (HI SO'S

'{' ^z H9'9 = f 'PS'S' (HAT '∞) 6ms'o ιοαο ο τ

(H6 'ra) S8-Z-88 "9' (HI 'ra) 0'9- £ ^

'(Η' «29 · 1-ε0 · ΐ '(Η9' ΖΗ9'9 = Γ 'Ρ) ^ · ΐ 1303 6 ΐ

·-6 Οΐ '(ΗΟΐ

'Ρ) 6Ζ'ΐ ιοαο ζ HS (HS' s) Ig-A '(Ηε' ω) ε SS'Z '(ΗΖΐ' m) SS-80.9 ιοαο 9 ΐ

3 '-6 9

(Ηΐ '«>) IO'S- IS' (m 's)

'V) n' \ ιοαο s ΐ

((ui d d) ί> coagulation) Η Ν Η ο Ν

6ΐ

880Z0 / T0df / X3d .Ϊ989 / Ϊ0 ΟΛ \ Table 2 (continued

N o .HNMR (solvent δ (p p m)

3 7 CDCl; 1.25 (d, J = 5.4Hz, 6H), 1.38 (s, 4H),

4.48-5.02 (m, 1H), 6.64-7.48 (m, 9H)

3 8 CDCl: 1.23 (d, J = 6.6Hz, 6H), 1.44 (s, 4H),

4.53-5.07 (m, 1H), 6.61-7.46 (m, 8H)

3 9 CDCl: 0.86-2.46 (m ₍ 14H), 1.20 (t, J = 6.6Hz, 3H),

3.20- 3.80 (m, 1H), 3.42 (q, J = 6.6Hz, 2H), 7.52 (m, 4H)

40 CDCl- 1.19 (d, J = 6.6Hz, 6H), 1.42 (s, 4H),

4.44-5.01 (m, 1H), 6.61-7.59 (m, 8H)

4 1 CDCl- 1.14 (t, J = 7.8Hz, 3H), 1.48-1.96 (m, 7H),

3.37 (q, J = 7.8Hz, 2H), 3.96 (brs, 2H),

4.85 (brs, 2H), 6.83-7.83 (m, 4H)

4 2 CDCl: 1.28 (d, J = 6.6Hz, 6H), 1.44 (s, 4H),

4.42-4.99 (m, 1H), 6.74-7.57 (m, 8H)

4 3 CDC1 _: 1.24 (d, J = 6.6Hz, 6H), 1.42 (s, 4H),

4.40- 5.01 (m, 1H), 6.74- 7.59 (m, 8H)

4 5 CDC1 _: 1.21 (d, J = 6.6Hz, 6H), 1.40 (s, 4H),

4.40-5.08 (m, 1H), 6.70-7.37 (m, 8H)

4 6 CDCl- 0.77-2.33 (m, 17H), 3.20-3.80 (m, 1H),

3.37 (q, J = 6.6Hz, 2H), 6.70-7.66 (m, 4H)

4 7 CDCl: 1.25 (d, J = 6.6Hz, 6H), 1.35 (s, 4H),

2.27 (s, 3H), 4.37 5.09 (m, 1H), 6.52- 7.61 (m, 9H)

4 8 CDCl: 1.22 (d, J = 6.6Hz, 6H), 1.39 (s, 4H),

2.29 (s, 3H), 4.39 5.00 (m, 1H), 6.53-7.40 (m, 8H)

4 9 CDCl: 0.45-2.60 (111, 17H), 2.27 (s, 3H), 3.10-4.45 (m, 3H),

7.14 (brs, 4H)

5 0 CDCl; 1.25 (d, J = 7.8Hz, 6H), 1.42 (s, 4H), 4.51-5.07 (m, 1H),

6.51-7.02 (m, 2H), 7.02-7.50 (m, 6H)

5 1 CDCl: 1.23 (d, J = 7.8Hz, 6H) 1.50 (s, 4H), 4.44-5.14 (m ₍ 1H),

6.48- 7.55 (m, 7H)

5 2 CDC1 _: 0.87- 2.31 (m, 14H), 1.20 (t, J = 6.6Hz, 3H),

3.20-3.80 (m, 1H), 3.50 (q, J = 6.6Hz, 2H), 6.74-7.39 (m, 3H) 53CDCl; 0.88-2.38 (m, 12H), 1.32 (d, J = 7.8Hz , 6H),

4.08-4.55 (m, 1H), 5.58 (brs, 1H), 7.35 (s, 5H) 54 CDCl; 1.23 (d, J = 7.8Hz, 6H), 1.46 (s, 4H), 4.44-5.02 (m , 1H),

6.66- 7.55 (m, 9H)

5 5 CDC1 _: 1.23 (d, J = 6.6Hz, 6H), 1.48 (s, 4H), 4.46-5.09 (m, 1H),

6.48- 7.55 (m, 8H)

5 6 CDC1 _: 1.29 (d, J = 6.6Hz, 6H), 1.46 (s, 4H), 4.29-4.99 (m, 1H),

6.27-7.53 (m, 8H)

5 7 CDCl: 1.25 (d, J = 6.6Hz, 6H), 1.44 (s, 4H), 4.37-5.00 (m, IH),

6.29-7.55 (m, 8H) Table 2 (continued)

H NMR (solvent δ (ρ ρ m))

5 8 CDC1: 0.92- 1.77 (m, 10H), 2.31 (s, 3H), 4.16-4.78 (m, 1H),

6.37- 7.50 (m, 8H)

5 9 CDC1: 1.09- 2.59 (m, 18H), 4.02-4.59 (m, 1H), 5.44-5.70 (m, 1H),

6.83- 7.58 (m, 4H)

6 0 CDC1 _: 0.79-2.64 (m, 15H), 2.64- 4.79 (m, 3H), 6.75-7.62 (m, 4H) 6 1 CDC1 _: 1.31 (d, J = 7.8Hz, 3H), 1.50-2.16 ( m, 10H),

2.88- 4.76 (m, 3H), 6.80- 7.55 (m, 4H)

6 2 CDC1 _; 1.21 (t, J = 6.6Hz, 3H), 1.54-2.03 (m, 7H),

3.54 (q, J = 6.6Hz, 2H), 4.01 (brs, 2H),

4.93 (brs, 2H), 6.79-7.59 (m, 4H)

6 3 CDC1 _; 1.21 (d, J = 7.5Hz, 6H), 1.38 (s, 4H), 4.43-5.13 (m, 1H),

6.33-7.53 (m, 8H)

6 4 CDC1: 1.19 (d, J = 6.6Hz, 6H), 1.43 (s, 4H), 4.43-5.20 (m, 1H),

6.48- 7.55 (m, 7H)

6 5 CDC1 _: 1.33 (t, J = 7.5Hz, 3H), 1.50-1.75 (m, 4H),

2.70-3.93 (m, 10H), 7.35 (s, 5H)

6 6 CDC1 _: 0.00-0.60 (m, 5H), 0.80 (s, 4H), 1.28 (d, J = 7.5Hz, 6H),

4 ・ 38-5.15 (m, 1H), 7.00-7.50 (m, 1H)

6 7 CDC1: 1.26 (d, J = 6.6Hz, 6H), 1.50 (s, 4H), 4.50-4.93 (m, 1H)

6.53- 7.57 (m, 7H)

6 8 CDC1 _: 1.35 (t, J = 6.6Hz, 3H), 1.50-1.81 (m, 4H),

2.64-3.15 (m, 4H), 3.15-4.02 (m, 4H),

3.59 (q, J = 6.6Hz, 2H), 6.90-7.48 (m, 4H)

6 9 CDC1 0.58- 2.23 (m, 9H), 0.85 (s, 4H), 1.23 (d, J = 7.5Hz, 6H),

4.35-5.08 (m, 1H), 7.03- 7.55 (m, 5H)

7 0 CDC1: 1.24 (d, J = 6.6Hz, 6H), 1.27-1.81 (m, '4H),

4.51- 4.98 (m, 1H), 6.72- 7.44 (m, 8H)

7 1 CDC1: 1.24 (d, J = 6.6Hz, 6H), 1.39-2.27 (m, 4H),

4.18-5.19 (m, 1H), 6.51-7.48 (m, 7H)

7 2 CDC1: 1.23 (d, J = 7.5Hz, 6H), 1.25-1.65 (m, 4H),

4.45-5.03 (m, 1H), 6.90- 7.78 (m, 8H)

7 3 CDC1: 1.19 (d, J = 7.5Hz, 6H), 1.13- 1.73 (m, 4H),

4.30-5.13 (m, 1H), 6.60-7.75 (m, 7H)

7 4 CDC1: 1.24 (d, J = 7.8Hz, 6H), 1.40 (s, 4H), 2.25 (s, 3H),

4.50-5.01 (m, 1H), 6.74-7.37 (m, 9H) Next, examples of the compounds included in the present invention are shown in Tables 4 and 4, including the compounds synthesized in the above Examples. Inventive compounds are not limited to these. However, the symbols in the table have the same meaning as described above. Table 3

1 O O no \

People _{Ν Λ Ν _Ν.}

N NΛ N,

N = N

N = N ^Et Enter ₀ 1 OO _o1 OO

义

NNN, CH ₂ C CH N = N ^Pr _ ^iS0 CH ₂ C

N = N

e

N = N

^-1 N people NN

N = N ^PMS0

N = N ^ET

Br

R L L

_{_{Ph CH 2 CH 2 Ph CHMe CH}} 2 Ph CMe 2 CH 2 Ph CMe 2 CHMe Ph CMe 2 CMe 2 Ph CHEt CH 2 Ph CEt 2 CH 2 Ph CHPr-n CH 2 Ph CHPr-iso CH 2 Ph CHBu-n CH 2 Ph CHBu-iso CH ₂ Ph CHBu-sec CH ₂ Ph CHBu-ter CH ₂ Ph CHF CH ₂ Ph CF ₂ CH ₂ Ph CHC1 CH ₂ Ph CC1 ₂ CH ₂ Ph CHCN CH ₂ Ph C (CN) ₂ CH ₂ Ph CHN0 ₂ CH ₂ Ph CH (N0 ₂ ) ₂ CH ₂ Ph CH (OMe) CH ₂ Ph C (0Me) ₂ CH ₂ Ph CHCF ₃ CH ₂ Ph C (CF ₃ ) ₂ CH ₂ H CHPh CH ₂

Me CHPh CH ₂

H CMePh CH ₂

H CHPh CHMe R ¹ LL

Me CMePh CH ₂

Me CHPh CHMe

H CMePh CHMe

Me CMePh CHMe

Me CMePh CMe ₂

Et CHPh CH ₂

H CEtPh CH ₂

H CHPh CHEt

_{_{_{Ph CMe 2 CHMeCH 2 Ph CMe 2}}} CMe 2 CH 2

H CMePh CH2CH2

H CHPh CHMeCH ₂

_{_{_{Ph CMe 2 CHMeCH 2 CH 2 Ph}}} CMe 2 CMe 2 CH 2 CH 2

H CMePh CH2CH2 CH2

H CHPh CHMeCH ₂ CH ₂

_{_{_{Ph CMe 2 CHMeCH 2 CH 2 CH}}} 2 Ph CMe 2 CMe 2 CH 2 CH 2 CH 2

H CMePh CH2CH2CH 2 CH2

H CHPh CHMeCH ₂ CH ₂ CH ₂

2-F-Ph CH ₂ CH ₂

2-F-Ph CHMe CH ₂

2-F-Ph CMe ₂ CH ₂

2-F-Ph CMe ₂ CHMe

2-F-Ph CMe ₂ CMe ₂

2-F-Ph CHEt CH ₂

2-F-Ph CEt ₂ CH ₂

2-F-Ph CF ₂ CH ₂

2-F-Ph CC1 ₂ CH, ^ t to o) Fh CPHMe- s

^ Is3 to

O o Or o o

R ¹ L ¹ L ²

H CH (4-F-Ph) CHMeCH ₂

Me CH (4-F-Ph) CH2 CH2CH2

H CMe (4-F-Ph) CH2CH2CH2

H CH (4-F-Ph) CHMeCH ₂ CH ₂

4-F-Ph CH ₂ CH2CH2CH2 CH2

4-F-Ph CHMe CH2CH2CH2CH2

4-F-Ph CMe 2 CH2CH2CH2 CH2

H CH (4-F-Ph) CH2CH2CH2CH2

Me CH (4-F-Ph) CH2CH2CH2CH2

H CMe (4-F-Ph) CH2CH2CH2CH2

2-Cl-Ph CH ₂ CH ₂

2-Cl-Ph CHMe CH ₂

2-Cl-Ph CMe ₂ CH ₂

2-Cl-Ph CMe ₂ CHMe

2-Cl-Ph CMe ₂ CMe 2

2-Cl-Ph CHEt CH ₂

2-Cl-Ph CEt ₂ CH ₂

2-Cl-Ph CF ₂ CH ₂

2-Cl-Ph CC1 ₂ CH ₂

2-Cl-Ph C (CN) ₂ CH ₂

H CH (2-Cl-Ph) CH ₂

Me CH (2-Cl-Ph) CH ₂

H CMe (2-Cl-Ph) CH ₂

H CH (2-Cl-Ph) CHMe

Me CMe (2-Cl-Ph) CH ₂

Me CH (2- Cl-Ph) CHMe

H CMe (2-Cl-Ph) CHMe

H CH (2-Cl-Ph) CHMeCH ₂

H CH (2-Cl-Ph) CH2CH2CH2

Me CH (2-Cl-Ph) CH2CH2CH2

H CMe (2- Cl-Ph) CH2 CH2CH2 CO t

O

n = s 3 S PC S a: s n: DC s e c s: n:

o o

* ~ 0 • "d ¾" ~ d • "d '" O "™ 0 * ™ 0 ^" ΰ * ~ 0 ^l- o ^μ "ΰ * ~ ^" ΰ * ~ ϋ "" d * τΰ ¾ cr cr

r ¹

) 22 ClPhesC CHMH- R ¹ L ¹ L

4-Cl-Ph CH ₂ CH ₂

4-Cl-Ph CHMe CH ₂

4- CI-Ph CMe ₂ CH ₂

4-Cl-Ph CMe ₂ CHMe

4-Cl-Ph CMe ₂ CMe ₂

4-Cl-Ph CHEt CH ₂

4-CI-Ph CE "CH ₂

4 -Cl-Ph CF ₂ CH ₂

4-Cl-Ph CC1 ₂ CH ₂

4-Cl-Ph C (CN) ₂ CH ₂

H CH (4-Cl-Ph) CH ₂

Me CH (4-Cl-Ph) CH ₂

H CMe (4-Cl-Ph) CH ₂

H CH (4-Cl-Ph) CHMe

Me CMe (4-Cl-Ph) CH ₂

Me CH (4-Cl-Ph) CHMe

H CMe (4-Cl-Ph) CHMe

H CH (4- Cl-Ph) CHMeCH ₂

4-CI- Ph CH ₂ CH 2 CH 2 CH 2

H CH (4-Cl-Ph) CH2 CH2CH2

Me CH (4- Cl-Ph) CH2 CH2CH2

H CMe (4-Cl-Ph) CH2 CH2CH2

H CH (4-Cl-Ph) CHMeCH ₂ CH ₂

4-C1- -Ph CH ₂ CH2CH2CH2CH 4-C1- -Ph CHMe CH2CH2CH2CH2 4-Cl-Ph CMe ₂ CH2CH2CH2CH2 H CH (4-C1-Ph) CH2 CH2 CH2CH

Me CH (4-Cl-Ph) CH2CH2CH2CH2 H CMe (4-Cl-Ph) CH2CH2CH2CH2

2-Br-Ph CH ₂ CH ₂

H CH (2-Br-Ph) CH ₂

H CH (2-Br-Ph) CH2 CH2CH2

2-Br-Ph CH ₂ CH2CH2CH2CH2 R ¹ L ¹ L ²

H CH (2-Br-Ph) CH2CH2CH2CH2

3-Br-Ph CH ₂ CH ₂

H CH (3-Br-Ph) CH ₂

3-Br-Ph CH ₂ CH 2 CH 2

H CH (3-Br-Ph) CH2CH2CH2

_{3-Br-Ph CH 2 CH2CH2} CH 2 CH2

H CH (3-Br-Ph) CH2CH2CH2CH2

4-Br-Ph CH ₂ CH ₂

H CH (4-Br-Ph) CH ₂

H CH (4-Br-Ph) CH2 CH2 CH2

4-Br-Ph CH ₂ CH2CH2CH2CH2

H CH (4-Br-Ph) CH2CH2CH2CH2

2-Me-Ph CH ₂ CH ₂

H CH (2-Me-Ph) CH ₂

H CH (2-Me-Ph) CH2CH2CH2

2-Me-Ph CH ₂ CH2CH2CH2CH2

H CH (2-Me-Ph) CH2CH2CH2CH2

3-Me-Ph CH ₂ CH ₂

H CH (3-Me-Ph) CH ₂

H CH (3-Me-Ph) CH2 CH2 CH2

3-Me-Ph CH ₂ CH2CH2CH2CH2

H CH (3-Me-Ph) CH2CH2CH2CH2

4-Me-Ph CH ₂ CH ₂

H CH (4-Me-Ph) CH ₂

H CH (4-Me-Ph) I, HI, H

H CH (4-Me-Ph) CH2CH2CH2

4-Me-Ph CH ₂ CH2CH2CH2CH2

H CH (4-Me-Ph) CH2CH2CH2CH2

2- CF ₃ -Ph CH ₂ CH ₂

H CH (2-CF ₃ -Ph) CH ₂

2- CF ₃ -Ph CH ₂ CH2CH2 tooo

R ¹ L ¹ L ²

H CH (4- MeO- Ph) CH2CH2CH2 CH2

2-CN-Ph CH ₂ CH ₂

H CH (2-CN-Ph) CH ₂

H CH (2-CN-Ph) CH2CH2CH2

2-CN-Ph CH ₂ CH2CH2CH2CH2

H CH (2-CN-Ph) CH2CH2CH2CH2

3-CN-Ph CH ₂ CH ₂

H CH (3-CN-Ph) CH ₂

H CH (3-CN-Ph) CH 2 CH2CH2

3-CN-Ph CH ₂ CH 2 CH 2 CH 2 CH 2

H CH (3-CN-Ph) CH2 CH2 CH2CH2

4-CN-Ph CH ₂ CH ₂

H CH (4-CN-Ph) CH ₂

H CH (4-CN-Ph) CH2 CH2 CH2

4-CN-Ph CH ₂ CH2 CH2CH2 CH2

H CH (4-CN-Ph) CH2 CH2 CH2CH2

2-N0 ₂ -Ph CH ₂ CH ₂

_{H CH (2-N0 2 -Ph} ) CH 2

_{_{2-N0 2 - Ph CH 2}} CH 2 CH 2

_{H CH (2- N0 2 - Ph} ) CH2 CH2CH2

_{_2-N0} 2 -Ph CH 2 CH2CH2CH2CH2

_{H CH (2- N0 2 -Ph)} CH2CH2CH2CH2

3-N0 ₂ -Ph CH ₂ CH ₂

_{H CH (3-N0 2 -Ph} ) CH 2

_{H CH (3-N0 2 -Ph} ) CH2 CH2 CH2

3-N0 ₂ -Ph CH ₂ CH2CH2CH2CH2

_{H CH (3- N0 2 -Ph)} CH2CH2CH2CH2

4-N0 ₂ -Ph CH ₂ CH ₂

_{H CH (4- N0 2 -Ph)} CH 2

4-N0 ₂ -Ph CH ₂ CH2CH2 R 1 L ¹ ²

_{H CH (4-N0 2 -Ph} ) CH2CH2 CH2

4- N0 ₂ -Ph CH ₂ CH2CH2CH2CH2

_{H CH (4-N0 2 -Ph} ) CH2CH2 CH2CH2

H cu (? I:! ノ CH ₂

H 4:!ー NO CH2 CH 2 CH2

2 4-C "-Ph 2 CH 2 CH 2 CH 2 CH 2

H PI

4: No CH 2 CH2CH2CH2

3, 5-C "-Ph pun 2 CH ₂

H ru n / ': P ΓΠh, no CH ₂

3, 5-Cl ₂ -Ph II. 2 CH2CH2

H n _t :! -ΓΠ ノ CH2 CH2

H: one runo CH2 CH2CH2

3, 5- CI ₂ -Ph 2 CH2CH2CH2CH2

H ΓΗ (: u no CH2CH2CH2CH2

2, 6-Cl ₂ -Ph CH. CH ₂

H fH (2 fi_r l; CH ₂

2, 6-Cl ₂ -Ph II. 2 CH2 CH2

H r fo ώ u runo CH2CH2

2, 6-Cl ₂ -Ph CH ₂ CH 2 CH 2 CH 2

H CH (2 6-C1;,-Ph) CH2 CH2 CH2

2 6-Cl ₂ -Ph CH ₂ CH2CH2CH2CH2

H CH (2, 6-C1;, -Ph) CH2 CH2 CH2CH2

2 '3-Cl ₂ -Ph CH ₂ CH ₂

_{H CH (2, 3- Cl:} ! -Ph) CH 2

H CH (2 3-CI:! -Ph) CH2CH2

2, 3-Cl ₂ -Ph CH ₂ CH2CH2CH2

H CH (2 3-Cl _: !-Ph) CH2 CH2CH2

2, 3- CI ₂ -Ph CH ₂ CH2CH2 CH2CH2

H CH (2, 3-CI: .-Ph) CH2CH2CH2CH2

2, 5- CI ₂ -Ph CH ₂ CH ₂

H CH (2, 5-CI; _2- Ph) CH ₂

H CH (2, 5-C1; ₂ -Ph) CH2 CH2

2, 5-Cl ₂ -Ph CH ₂ CH2CH2 CH2

H CH (2, 5-C1; `` Ph '' CH2 CH2 CH2

2, 5- CI ₂ -Ph CH ₂ CH2CH2 CH2CH2 1

RL ¹ L ²

H CH (2, 5-Cl ₂ : -Ph) CH2CH2CH2CH2

2, 4-F ₂ -Ph CH ₂ CH ₂

H CH (2, 4-F _2- • Ph) CH ₂

2, 4-F ₂ -Ph CH ₂ CH2 CH2

H CH (2, 4-F ₂ -Ph) CH2 CH2

2, 4-F ₂ -Ph CH ₂ CH2 CH2 CH2

H CH (2, 4-F ₂ -Ph) CH 2 CH 2 CH 2

2, 4-F ₂ -Ph CH ₂ CH2CH2CH2CH2

H CH (2, 4-F ₂ -Ph) CH 2 CH 2 CH 2 CH 2

3, 5-F ₂ _Ph CH ₂ CH ₂

H CH (3, 5-F ₂ -Ph) CH ₂

H CH (3, 5-F ₂ -Ph) CH2CH2

3, 5-F ₂ _Ph CH ₂ CH 2 CH 2 CH 2

H CH (3, 5-F ₂ -Ph) CH2CH2CH2

3, 5-F ₂ -Ph CH ₂ CH2CH2CH2CH2

H CH (3, 5-F ₂ -Ph) CH2 CH2CH2 CH2

2- F-4-Cl-Ph CH ₂ CH ₂

H CH (2- F- 4- Cl-Ph) CH ₂

H CH (2-F-4-Cl-Ph) CH2CH2

2- F-4-Cl-Ph CH ₂ CH2 CH2 CH2

H CH (2-F-4-Cl -Ph) CH2 CH2CH2

2- F-4-Cl-Ph CH ₂ CH 2 CH 2 CH 2 CH 2

H CH (2-F-4-Cl -Ph) CH 2 CH 2 CH 2 CH 2

2, 4-Me ₂ -Ph CH ₂ CH ₂

H CH (2, 4-Me ₂ — Ph) CH ₂

H CH (2, 4-Me ₂ -Ph) CH2CH2

2, 4-Me ₂ -Ph CH ₂ CH2CH2CH2

H CH (2, 4-Me ₂ -Ph) CH2 CH2 CH2

2, 4-Me ₂ -Ph CH ₂ CH2CH2CH2CH2

H CH (2, 4-Me ₂ -Ph) CH2 CH2 CH2CH2

3, 5-Me ₂ -Ph CH ₂ CH ₂

H CH (3, 5-Me ₂ -Ph) CH ₂

3, 5-Me ₂ -Ph CH ₂ CH 2 CH 2

H CH (3, 5-Me ₂ -Ph) CH2CH2

3, 5-Me ₂ -Ph CH ₂ CH 2 CH 2 CH 2

H CH (3, 5-Me ₂ -Ph) CH2CH2 CH2

3, 5-Me ₂ -Ph CH ₂ CH2 CH2CH2 CH2

H CH (3, 5-Me ₂ -Ph) CH2CH2 CH2CH2

2, 6-Me ₂ -Ph CH ₂ CH ₂

H CH (2, 6- Me ₂ -Ph) CH ₂

2, 6- Me ₂ -Ph CH ₂ CH2CH2 R ¹ L ¹ L ²

H CH (2, 6 · -Me 2: -Ph) CH2CH2

2, 6- Me ₂ --Ph CH ₂ CH2 CH2 CH2

H CH (2, 6- -Me ₂ ; -Ph) CH2 CH2CH2

2, 6-Me ₂ --Ph CH ₂ CH2CH2 CH2CH2

H CH (2, 6- -Me ₂ `` Ph '' CH2 CH2 CH2 CH2

2, 3- Me ₂ --Ph CH ₂ CH ₂

H CH (2, 3- -Me ₂ : -Ph) CH ₂

H CH (2, 3- -Me ₂ ; -Ph) CH2CH2

2, 3- Me ₂ --Ph CH ₂ CH2CH2CH2

H CH (2, 3 · -Me 2: -Ph) CH2 CH2 CH2

2, 3- Me ₂ --Ph CH ₂ CH2CH2CH2CH2

_{H CH (2, 3- -Me 2} : -Ph) CH2CH2CH2CH2

2, 5- Me ₂ --Ph CH ₂ CH ₂

H CH (2, 5- -Me ₂ : -Ph) CH ₂

H CH (2, 5- -Me ₂ Ph) CH2CH2

2, 5- Me ₂ --Ph CH ₂ CH2 CH2 CH2

H CH (2, 5- -Me ₂ : -Ph) CH2CH2CH2

2, 5-Me ₂ --Ph CH ₂ CH2CH2CH2CH2

H CH (2, 5- -Me ₂ -Ph) CH2CH2CH2CH2

2-Cl-6-F-Ph CH ₂ CH ₂

2-EtO-Ph CH ₂ CH ₂

3-EtO-Ph CH ₂ CH ₂

4-EtO-Ph CH ₂ CH ₂

Pr-cyc CH ₂ CH ₂

Bu-cyc CH ₂ CH ₂

Pen-eye CH ₂ CH ₂

Hex-eye CH ₂ CH ₂ Thiophene- _2- yl CH ₂ CH ₂

3-Chlorothiphen-2-yl CH ₂ CH ₂

4-chlorothiophene 2-yl CH ₂ CH ₂

5—Chlorothi phen-1-one CH ₂ CH ₂

3,4-Si * Chlorothi-phen-2-yl CH ₂ CH ₂

3,5-Chlorothiphen-2-yl CH ₂ CH ₂

4, 5-Si * Chlorothiophene 2-yl CH ₂ CH ₂

3,4,5-tric π rochi-san 2--2-yl CH ₂ CH ₂

3-F * Mouth chin- 2-CH ₂ CH ₂

4 1 ^ ^! Mochiofen 2-yl CH ₂ CH ₂

5-mouth fen- 2- CH ₂ CH ₂

Thiofen-3-yl CH ₂ CH ₂

2-pi-rotiophen-3-yl CH ₂ CH ₂

4-arc ππ-thick phen-one 3-yl CH ₂ CH ₂

5-q π-rotiophen-3 -yl CH ₂ CH ₂ R ¹ LL

2.4-sq nn thiophen-3-yl CH ₂ CH ₂ 2,5-sq. Rotifen-3-yl CH ₂ CH ₂

4.5-S ', ππ thiophene in-3-yl CH ₂ CH ₂ 2,4,5-tric ππ thiophene-3-yl CH ₂ CH ₂ furan ₂ -yl CH ₂ CH ₂ furan-3 - I le CH _₂ CH ₂ fire. π-le-1-yl CH ₂ CH ₂ h 'mouth-2- yl CH ₂ CH ₂ h' π-le -3-yl CH ₂ CH ₂ Oxa, CH-CH ₂ CH ₂ old Kisaso '--4-I le CH ₂ CH ₂ Okisaso "- le - 5- I le CH ₂ CH ₂ thia Shikabane - Le - 2-I le CH ₂ CH ₂ Chiaso' --4- I Le CH ₂ CH ₂ thia ,, one rule 5 I le CH ₂ CH ₂ Imi gamma source '- Le - 1 - I le CH ₂ CH ₂ Imi gamma' Shikabane - Le - 2-I le CH ₂ CH ₂ Imita '' Shikabane --4-I le CH ₂ CH ₂ Imi gamma '厂--5-I le CH ₂ CH ₂ Isookisaso "- le - 3- I le CH ₂ CH ₂ Isookisa' Shikabane - le - 4- I le CH ₂ CH ₂ Isookisa, Shikabane - Le - 5-I le CH ₂ CH ₂ Isochia 'Shikabane - Le - 3-I le CH ₂ CH ₂ Isochiaso "- le - 4 I) les CH ₂ CH ₂ Isochia' Pas - Le -. 5 I le CH ₂ CH ₂ arsenide La 'Pearl -. 1-I le CH ₂ CH ₂ arsenide la'厂one rule 3 I le CH ₂ CH ₂ Biraso ', - Le - 4 I le CH ₂ CH ₂ Villa 'Society—Ru 5-yl CH ₂ CH ₂

1-Methyl-3,5-si * Chlorovilla (4-yl) CH ₂ CH ₂

1-Methyl-5-chlorophenol-yl-4-yl CH ₂ CH ₂ 1-methyl-5-chloro- mouth Rasso'-le-4-yl CH ₂ CH ₂

1,3,4-oxa-yl 2-yl CH ₂ CH ₂

1,3, 4-thia § 'Shikabane - Le - 2 - I le CH ₂ CH ₂

1,3,4-tria-1-yl CH ₂ CH ₂

1,3,4-triazo'-yl- ₂ -yl CH ₂ CH ₂ 1, 2,4-oxo'-yl-yl-3-yl CH ₂ CH ₂

1,2,4-oxacin'as'-yl-5-yl CH ₂ CH ₂

1,2,4-thia 'Aso'-yl-3 -yl CH ₂ CH ₂

1,2,4-thiasi ', al-5-yl CH ₂ CH ₂

1,2,4-trier, social 1-yl CH ₂ CH ₂ 1, 2,4-trier, par-3-yl CH ₂ CH ₂

1,2,4-Tri-Par-5-yl CH ₂ CH ₂

1, 2,3-oxasyl-yl- 4-yl CH ₂ CH, R ¹ L ¹ L ²

1,2,3-year-old 'ass' -le -5-yl CH ₂ CH ₂

1,2,3-chia'a 'pearl-3-yl CH ₂ CH ₂

1,2,3-chia 'a' pearl one 5-yl CH ₂ CH ₂

1,2,3,4-Tetra-yl-1-yl CH ₂ CH ₂

1,2,3,4-tetra, val-5-yl CH ₂ CH ₂

1,2,3,5-tetra, val-1-yl CH ₂ CH ₂

1, 2, 3, 5 - tetra, Pearl - 4 I le CH ₂ CH ₂ arsenate 'Rishi' emissions - 2-I le CH ₂ CH ₂ Pirishi 'emissions - 3-I le CH ₂ CH ₂ arsenate' Rishi ' CH 4 CH ₂ CH ₂

2, 6 - sheet 'black hole Rishi' down-4-I le CH ₂ CH ₂ Pirimishi 'down-2- I le CH ₂ CH ₂ Rimishi' down-5- I le CH ₂ CH ₂ Pirimishi * emission 4- I'm CH ₂ CH. Rashi'n_2-yl CH ₂ CH ₂ h. Rita's -3-yl CH ₂ CH ₂ HI 'Rita' 4-yl CH ₂ CH ₂

1,3,5-triazine * 2-yl CH ₂ CH ₂

1,2,4-triazine-3-yl CH ₂ CH ₂

1,2,4-triazine-5-yl CH ₂ CH ₂

1,2,4-triazine-6-yl CH ₂ CH ₂ Table 4

880Z0 / T0df / X3d .Ϊ989 / Ϊ0 OAV

8 ^

880Z0 / T0df / X3d .Ϊ989 / Ϊ0 OAV

6

Z0 / T0df / X3d .Ϊ989 / Ϊ0 OAV i?

OS

Z0 / T0df / X3d .Ϊ989 / Ϊ0 OAV RR ¹

Me Et

Me Pr-n

Me Pr-iso

Me Bu-iso

Me Bu-sec

Me Bu-ter

Me CHMeCHMe ₂ Me Pen-n

Me Hex- i so

Me Pr-cyc

Me Bu-cyc

Me CH ₂ Pr-eye Me CH ₂ Bu-eye Me CH ₂ Pen-cyc Me CH ₂ Hex-cyc Me CH ₂ CH ₂ Pr-cyc Me CH ₂ CH = CHMe

Me CH ₂ C≡CMe Me CH ₂ 0Me

Me CH ₂ 0Et

Me CH ₂ 0Pr-n Me CH ₂ 0Bu-n Me CH ₂ 0Bu-iso Me CH ₂ 0Bu-sec Me CH ₂ 0Bu-ter Me CH ₂ CH ₂ 0Me Me CH ₂ CH ₂ 0Et Me CH ₂ CH ₂ 0Pr-n Me CH ₂ CH ₂ CH ₂ 0Me Me CH ₂ CH ₂ CH ₂ 0Et Me CH ₂ CH ₂ CH ₂ CH ₂ 0Me Me 2- Cl-Ph

Me 3- Cl-Ph

Me 4- Cl-Ph

Me 2, 4-Cl ₂ _Ph Me 3, 5-Cl ₂ -Ph Me 2, 6-C -Ph Me 2, 3-Cl ₂ -Ph Me 2, 5-Cl ₂ _Ph Me 2- F-Ph

Me 3- F-Ph

Me 4- F-Ph

Me 2-F-4-C1-Ph Me 2-Br-Ph RR

Me 3-Br- Ph

Me 4- Br-Ph

Me 2- Me- Ph Me 3- Me-Ph

Me 4- Me-Ph

_{Me 2, 4-Me 2 -Ph} Me 3, 5- Me 2 one _{Ph Me 2, 6-Me 2} -Ph Me 2, 3-Me 2 one _{Ph Me 2, 5-Me 2} -Ph Me 2- MeO- Ph Me 3- MeO-Ph

Me 4- MeO-Ph

Me 2- CF ₃ — Ph Me 3- CF ₃ — Ph Me 4- CF ₃ — Ph

Me 2, 4, 6-Cl ₃ -Ph Me 2, 3, 5-Cl ₃ — Ph Me 2, 3, 4-Cl ₃ -Ph Me 2- N0 ₂ — Ph Me 3- N0 ₂ N0 ₂ -Ph Me 2- CN-Ph Me 3- CN-Ph Me 4- CN-Ph

Me CH ₂ Ph

Me OMe

Me OEt

Me OPr-n

Me OBu-n

Me OBu-iso

Me OBu-sec Me OBu-ter Et Bu-n

Et Bu-iso

Et Bu-sec

Et Bu-ter

Et CHMeCHMe Et Pen-n

Et Hex-n

Et Hex- i so Et Pr-cyc

Et Bu-cyc

Et CH ₂ Pr-cyc Et CH ₂ Bu-cyc R ¹ R ¹

Et CH ₂ Pen-cyc Et CH ₂ Hex-cyc Et CH ₂ CH ₂ Pr-eye

Et CH ₂ CH = CHMe Et CHsCHsCH-CHs Et CH2C Three CH

Pr-n Bu-n

Pr-n Pen-n

Pr-n Hex-n

Pr-n

Pr-n CH ₂ Cho CH Bu-n Pen-n

Bu-n Hex-n

Bu-n CH ₂ C≡CH

CH2 CH = CH CH ₂ C

Me CH ₂ SMe

Me CH ₂ SEt

Me CH ₂ SPr-n

Me CH ₂ SBu-n

Me CH ₂ sBu-iso

Me CH ₂ t> Bu-sec

Me CH ₂ SBu-ter

Me CH ₂ CH ₂ SMe

Me CH ₂ CH ₂ SEt

Me CH ₂ CH ₂ SPr-n

Me CH ₂ CH ₂ CH ₂ SMe

Me CH ₂ CH ₂ CH ₂ CH ₂ SMe

Et 4-Cl-Ph

Et 2, 4-Cl ₂ _Ph

Et 3, 5- C1: -Ph

Et 2, 6- Cl: -Ph

Et 2, 3-CI: -Ph

Et 2, 5-C1; _Ph

Et 3-F-Ph

Et 2- F- 4-Cl- Ph

Et 2- Br-Ph

Et 3- Br-Ph

Et 4-Br-Ph

Et _2, 4- Me 2 one Ph

Et 3, 5-Me ₂ one Ph

Et 2, 6-Me ₂ -Ph

Et 2, 3-Me ₂ _Ph R ¹ R ¹³

Et 2, 5-Me ₂ -Ph

Et 2-MeO-Ph

Et 3-MeO-Ph

Et 4-MeO-Ph

Et 2-CFs-Ph

Et 3-CF ₃ -Ph

Et 4-CF ₃ -Ph

Et 2, 4, 6-Cl ₃ -Ph

Et 2, 3, 5-Ch-Ph

Et 2, 3, 4-Cl ₃ -Ph

Et 3-N0 ₂ -Ph

Et 2-CN-Ph

Et 3-CN-Ph

Et 4-CN-Ph

Pr- ISO 2, 4-Cl ₂ -Ph

Pr- ISO 3, 5-Cl ₂ — Ph

Pr- ISO 2, 6-Cl ₂ -Ph

Pr- ISO 2, 3-Cl ₂ _Ph

Pr-ISO 2, 5-Cl ₂ -Ph

Pr- ISO 2- F- 4-Cl-Ph

Pr- ISO _2, 4- Me 2 one Ph

Pr- ISO 3, 5-Me ₂ _Ph

Pr-ISO 2, 6-Me ₂ _Ph

Pr-ISO 2, 3-Me ₂ _Ph

Pr- ISO 2, 5-Me ₂ -Ph

Pr-ISO 2, 4, 6-Cl ₃ -Ph

Pr- so 2 3 5-C1, Ph

Pr-ISO 2, 3, 4-C -Ph

Pr-ISO 2-N0 ₂ — Ph

Pr-ISO 3-N0 ₂ — Ph

Pr- ISO 4-N0 ₂ -Ph

Pr- ISO 2-CN-Ph

Pr- ISO 3-CN-Ph

Pr- ISO 4-CN-Ph

As a continuation of Table 4, mentioned example of configuring a monitor ring and the nitrogen atom to which R ¹² and R ¹³ is attached below.

Z0 / I0df / X3d .Ϊ989 / Ϊ0 OAV The amount of the compound of the present invention applied as a herbicide varies depending on the application scene, application time, application method, weeds and cultivated crops, but generally, the amount of active ingredient is hectare. About 0.001 to 50 kg, preferably about 0.01 to 10 kg per (ha) is suitable.

The compound of the present invention can be used as a herbicide for paddy fields in any of soil treatment and foliage treatment under harbor water. Examples of paddyweeds include paddyweeds (Al ismacanal iculatum), omodaka '(Sag tariatrifol ia), and pericae (Sagittariapygmaea). (Cyperusserot inus), Cyperaceae weed (Scirpusjuncoides), and Eleochariskuroguwai (Eleochariskuroguwai); ), Potamogetondi stinctus (Potamogetondi stinctus), Potamogetonaceae weeds (Rotattadica), Lythraceae (Lythraceae) and Lythraceae (Rosaceae), such as Rotalaindica -galli) Weeds (Gramineae) Weeds And the like. In addition, the compound of the present invention can be used as a herbicide for upland fields in any of soil treatment, soil admixture treatment, and foliage treatment. It can also be applied to the control of various weeds on non-agricultural land such as athletic fields, open spaces and track ends.

If necessary, the compound of the present invention may be mixed with other kinds of herbicides, various insecticides, fungicides, plant growth regulators, synergists and the like at the time of preparation or spraying.

In particular, by applying a mixture with other herbicides, it is possible to expect a low cost reduction due to a decrease in the amount of applied medicine, an increase in the herbicidal spectrum due to the synergistic action of the mixture, and a higher herbicidal effect. . At this time, a combination with a plurality of known herbicides is possible at the same time. Preferred herbicides to be used in combination with the compound of the present invention include, for example, pyrazosulfuron-ethylZ (common name), bensulfuron-methyl (common name), and sinosulfuron / common name. Name), imazosulfuron (—common name), azimsulfuron (azimsulfuron general) Name), halosulfuron-methyl (halosulfuron-methyl / -generic name), pretilachlor (pretilachlor-generic name), esprocarb (esprocarbZ-generic name), virazolate (pyrazolate-generic name), virazoxyfen (pyrazoxyfen-generic name) ), Benzofenap (benzofenap / —common name), Daimron (daimuron no common name), promobutide (bromobutideZ—common name), nabroanilide (naproani 1 ideZ—common name), clomeprop (clomepropZ—common name), C NP (generic name), chrometoxinil (chlomethoxynil / generic name), bifenox (bi fenox / —generic name), oxadiazon (oxadiazonZ—generic name), oxadiaargyl (generic name), cafuenstrol (cafenstrole-) Generic name), oxazic lomefoneZ (generic name), indanofan (indanofan / —generic name), pentoxa Zon (pentoxazone-general name), pyriminobac-methylZ (common name), cyhalofop-butylZ (common name), phen tolazamide (fentrazamide-common name), mefenacet (mefenacet) Generic name), butachlor (butachlor / —generic name), butenachlor (butenachlorZ—generic name), dithiopyl (dithiopyl / —generic name), benfuresate (benfuresate / —generic name), pyributicarb (pyributicarbZ—generic name) Name), benthiocarb (benthiocarb-generic name), dime pipette (dimepiperate generic name), molinete (molinateZ—generic name), pig mifos (butami fosZ—generic name), kink mouth rack (quinclorac-generic name) ), Simmethrin (cinmethyl in-generic name), simetrin (simetryn / —generic name), benzulide (bensulide / —generic name), dimethamethrin (dimet) hametryn (common name), MCPA, MCPB, etobenzanid (etobenzani d), cumyluron (cumyluron / —common name), tenylchlor (thenylchlorZ—common name), ethoxysulfuron (ethoxysulfuron / —common name), kinokurami (Quinoclamine / generic name), benzobicyclon / (generic name), pyriftalid (pyrifta lid / —generic name), bispyribac, HSA-961 (test name), anilofos (anilofos / generic name) No.) and 0K-701 (test name).

When the compound of the present invention is applied as a herbicide, it is generally mixed with an appropriate solid carrier or liquid carrier, and further, if desired, a surfactant, a penetrant, a spreading agent, a thickener, an antifreezing agent. Agent, binder, anti-caking agent or anti-decomposition agent, etc., in any dosage form such as liquid, emulsion, wettable powder, dry flowable, flowable, powder or granule It can be put to practical use.

In addition, from the viewpoint of labor saving and improvement of safety, the preparation of any of the above dosage forms can be provided by being enclosed in a water-soluble package.

As a solid carrier, for example, kaolinite, ノ, and others. Natural minerals such as irophyllite, sericite, talc, bentonite, acid clay, attapulgite, zeolite and diatomaceous earth; inorganic salts such as calcium carbonate, ammonium sulfate, sodium sulfate and potassium chloride; Synthetic silicic acid, synthetic silicate and the like can be mentioned.

Examples of the liquid carrier include water, alcohols (ethylene glycol, propylene glycol, isopropanol, etc.), aromatic hydrocarbons (xylene, alkyl benzene, alkyl naphthalene, etc.), ethers (butyl sorbitol). etc.), Quai tons acids (Kisano down like cyclohexane), esters _(y _ Puchiroraku tons, etc.), acid Ami earth (N _ Mechirupirori Don, N- Okuchirupirori dong, etc.) and vegetable oils (soybean oil, rapeseed oil, Cottonseed oil, castor oil, etc.).

These solid and liquid carriers may be used alone or in combination of two or more. Examples of the surfactant include polyoxyethylene alkyl ether, polyoxyethylene styrylphenyl ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, and the like. Non-ionic surfactants such as polyoxyethylene sorbitan fatty acid esters, and alkyl benzene sulfonates, lignin sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, alkyl naphthalene sulfonates, and naphthalene sulfonates Salts of formalin condensates of: formalin condensates of alkylnaphthalenesulfonic acids; polyoxyethylene alkylaryl ethersulfate or phosphate; polyoxyethylenestyrylphenylethersulfate Or ionic surfactants such as phosphates and alkylamine salts. Although the content of these surfactants is not particularly limited, it is usually desirable that the content be in the range of 0.05 to 20 parts by weight based on 100 parts by weight of the preparation of the present invention. These surfactants may be used alone or in combination of two or more.

Next, a formulation example of a preparation when the compound of the present invention is used is shown. However, the composition examples of the present invention are not limited only to these. In the following formulation examples, "parts" Means parts by weight.

(Wettable powder)

Compound of the present invention 0.1 to 80 parts

Solid carrier 5 to 98.9 parts

Surfactant 1 to 10 parts

Others 0 to 5 copies

Other examples include anti-caking agents, anti-decomposition agents, etc. (emulsions)

0.1 to 30 parts of the compound of the present invention

Liquid carrier 55 to 95 parts

Surfactant 4, 9 to 15 parts

(Floable agent)

0.1 to 70 parts of the compound of the present invention

Liquid carrier 15 to 98.8 9 parts

Surfactant 1 to 12 parts

Other 0.0 0.03

Other examples include antifreezing agents and thickeners (dry flowables)

0.1 to 90 parts of the compound of the present invention

Solid carrier 0 to 98.9 parts

Surfactant 1 to 20 parts

Others 0 to 10 copies

Other examples include a binder and a decomposition inhibitor. (Liquid)

Compound of the present invention 0.01 to 30 parts

Liquid carrier 0.1 to 50 parts

Water 50 to 9.8 9 parts

Others 0 to 10 copies

Others include, for example, antifreezing agents, spreading agents, and the like. (Granules)

Compound of the present invention 0.01 to 10 parts

Solid support 90 ~ 9 9.9 9 parts

Others 0 to 10 copies

Other examples include a binder and a decomposition inhibitor. When using, apply the above preparations as they are or after diluting them 1- to 1000-fold with water. Formulation examples ''

Next, specific examples of agrochemical preparations containing the compound of the present invention as an active ingredient are shown, but the invention is not limited thereto. In the following formulation examples, “parts” means parts by weight.

(Formulation example 1) wettable powder

Compound of the present invention No. 120 parts

Pyrophile Light 7 6 parts

Solpole 5 0 3 9 2 parts

(Mixture of nonionic surfactant and anionic surfactant: trade name of Toho Chemical Industry Co., Ltd.)

Carplex # 8 0 2 copies

(Synthetic hydrous silicic acid: Shionogi & Co., Ltd. product name)

The above is uniformly mixed and pulverized to obtain a wettable powder.

(Formulation Example 2) Milk

Compound of the present invention No. 15 parts

Xylene 7 5 parts

N-methylpyrrolidone 15 parts

Solpole 2 6 8 0 5 parts

The above are uniformly mixed to form an emulsion. (Compounding Example 3) Flowable agent

Compound of the present invention N 0.125 parts

Agrisol S- 7 1 0 1 0

(Nonionic surfactant: Kao Corporation)

Lunox 1 0 0 0 C 0.5 part

(Anionic surfactant: Toho Chemical Industry Co., Ltd.)

Xanthan gum 0.0 2 parts

Water 6 4. 4 8 parts

After uniformly mixing the above, wet pulverization is performed to obtain a flowable agent.

(Formulation Example 4) Dry flowable agent

Compound of the present invention N 0.175 parts

Hytenol NE— 1 5 5 parts

(Anionic surfactant: Daiichi Kogyo Pharmaceutical Co., Ltd.)

No, 'Nirex N10

(Anionic surfactant: Nippon Paper Industries Co., Ltd.)

Power plex # 8 0 1 0

(Synthetic hydrous silicic acid: Shionogi & Co., Ltd. product name)

After uniformly mixing and pulverizing the above, a small amount of water is added, and the mixture is kneaded with stirring, kneaded, granulated by an extrusion granulator, and dried to obtain a dry flowable agent.

(Formulation Example 5) Granules

Compound of the present invention No. 1 1 part

Bentonite 5 5 parts

Talc 4 4 parts

After the above mixture is uniformly mixed and pulverized, a small amount of water is added, and the mixture is kneaded with stirring, kneaded, granulated by an extruder and dried to obtain granules.

(Formulation Example 6) Granules

Compound of the present invention No. 1 part

Compound (A) 0.0 7 parts

DBSN 3 copies Epoxidized soybean oil 1 part

Bentonite 30

Talc 6 4.9 3 parts

The above compound (A) means pyrazosul furon-ethyl (generic name), and DBSN means sodium dodecylbenzenesulfonate.

Next, the usefulness of the compound of the present invention as a herbicide will be specifically described in the following test examples.

(Test Example 1) Herbicidal effect test by weed pre-treatment under flooded conditions

3 3. After filled with alluvial soil in 3 cm ² styrol cup, and mixed Pour water was submerged condition of water depth 4 cm. The seeds of Nobie, Firefly and Konagi were mixed and sown in the above-mentioned cups, and rice seedlings at the 2.5 leaf stage were transplanted. Place the cup in a greenhouse at 25 to 30 ° C, and dilute the water-dispersible powder of the compound of the present invention prepared according to Formulation Example 1 with water so that the prescribed dose is reached on the water surface on the day after seeding. And processed. Three weeks after the treatment, the herbicidal effect on rice and various weeds was investigated. 0 is less than 5% wither, 1 is 5% or more and less than 25 96 wither, 2 is 25% or more and less than 50% wither, 3 is 50% or more and less than 75% wither, 4 is 7 5 to 5% is a 5-point rating indicating that withering occurs, and 95% or more indicates withering. Table 5 shows the results.

(Test Example 2) Herbicidal effect test by weed growing season treatment under flooded conditions

3 3. After filled with alluvial soil in 3 cm ² styrol cup, and mixed Pour water was submerged condition of water depth 4 cm. The seeds of Nobie, Firefly and Konagi were mixed in the above cups. The cups are placed in a greenhouse at 25 to 30 ° C to grow the plants, and when the flour, fireflies, and pearls have reached the 1-2 leaf stage, they are blended so that the prescribed dose is applied to the water surface. A wettable powder of the compound of the present invention prepared according to Example 1 was diluted with water and treated. Three weeks after the treatment, the herbicidal effect on various weeds was investigated in accordance with the criteria in Test Example 1. The results are shown in Table 6.

(Test Example 3) Herbicidal effect test by soil treatment

Put the sterilized flood soil in a plastic box 21 cm long, 13 cm wide and 7 cm deep, Heno cologza, oats, blackgrass, soybean, and soybean seeds are each sown in spots, covered with a soil of about 1.5 cm, and then compacted to the soil surface so that the active ingredient content is at a specified ratio. Sprayed evenly with a spray. As a chemical solution at the time of spraying, a wettable powder appropriately prepared in accordance with Formulation Example 1 was used by diluting with water and sprayed over the entire surface. Three weeks after the application of the drug solution, the herbicidal effect on the plants was examined according to the criteria in Test Example 1. Table 7 shows the results.

The symbols in each table have the following meanings.

A (Nobie), B (Firefly), C (Eel), D (Eno Korogusa), E (Eelgrass), F (Blackgrass), a (Transplanted rice), b (Soybean), c (Pota) Table 5 Chemicals Kuchiyanagi Treatment dose Herbicidal effect

No. g / a A B C a

1 2.52 5 5 5 0

2 2.52 5 5 5 1

3 2.52 5 5 5 1

4 2.52 5 5 5 0

5 2.52 5 4 4 0

6 2.52 5 4 5 0

7 2.52 5 5 4 0

8 2.52 5 4 4 0

9 2.52 5 4 4 0

10 2.52 5 5 5 0

11 2.52 5 5 4 0

12 2.52 5 4 4 0

13 2.52 4 3 3 0

14 2.52 5 5 5 3

15 2.52 5 5 5 3

16 2.52 5 5 5 0

17 2.52 5 5 5 2

18 2.52 5 5 5 0

19 2.52 5 3 5 0

20 2.52 5 3 3 1

21 2.52 5 4 5 0

22 2.52 5 5 5 1

23 2.52 5 4 5 0

24 2.52 5 5 5 1 Table 5 (continued)

ο "INNT η U. A B 3.

ς 5 3 0

j π U ώaΌ 5 5 0 u

97 5 5 c

0π 9Q 5 5 0

on

L * 5 5 9

0 U L. L 5 5 π U ύ 5 4 0

0 π U

0

* Ό 5 5 π u ο 5 5

0 C. 5 5 0

2 52 5 4 fl

2 2 5 5 o

2 2 5 4 o * 5 4 fl

Peri 5 5 o

41 5 5 o

42 2 S2 5 5

5 5 2 οκ ♦ ϋ 5 5

40 L 0ώ 5 5 n u

A 7 5 5 0 π ¾o 5 4 D n u

¾y 5 4 D u

5 5

Ό 5 5 0

5? 0 Οώ 5 4 0 yj

5 5 «j o

35 54 2.52 5 5 5 o

55 2.52 5 5 5 o

ΌΌ * Ό ά 5 5 o

57 2.52 5 5 5 0

58 2.52 5 4 5 0

40 59 2.52 5 5 5 0

60 2.52 5 5 5 0

61 2.52 5 5 5 0

62 2.52 5 5 5 0

63 2.52 5 5 5 0

45 64 2.52 5 5 5 0

65 2.52 5 5 5 3

66 2.52 5 5 5 3 Table 5 (continued)

Treatment amount Herbicidal effect

N U. G / a A B Q

Ό / 2.52 5 5 o

00 2.52 5 5 c.

2.52 5 5 9 d

7 / ΠU 2.52 5 3 A o \ J

71 2.52 5 4 5 0

72 2.52 5 4 4 0

73 2.52 5 5 4 0

74 2.52 5 5 5 0

75 2.52 5 5 5 0

76 2.52 5 4 4 1

77 2.52 5 5 1

78 2.52 5 5 5 1

79 2.52 5 5 0

80 2.52 5 5 5 2

Table 6

Compound Treatment dose Herbicidal effect

No. g / a A B C

1 2.52 4 3 3

2 2.52 4 2 3

3 2.52 4 3 3

4 2.52 4 3 3

5 2.52 4 2 2

6 2.52 4 3 3

7 2.52 4 2 2

8 2.52 3 2 2

9 2.52 2 0 0

10 2.52 4 3 3

11 2.52 4 2 2

12 2.52 4 3 3

13 2.52 3 2 2

14 2.52 4 2 2

15 2.52 4 2 2

16 2.52 4 2 2

17 2.52 4 2 2

18 2.52 4 1 2 Table 6 (continued) Amount of chemicals treated Herbicidal effect κ IN U. G / a

1 QO "9 * J 4 2 9 0 ώ 9 · £; 9 1 0 n

91 9 ώ4 2 2

¾ 9 ώ 4 2

OA 9 S 4 3 A ύ 0.c) 0 2 0

0 L .4 3 丄 0 L 07 ώ .4 3 0 Q

C O

ώ OθQ L. ώ 4 3 0 Q

OQ 0 C O

ύ, 4 3 0 W 9 C O 4 2 L 0 ΐ 0

丄 L. C 4 3 0

ΟΛ 00

Δ \ 3 ά 0 L. 4 3 0

0

00 0

00 L. 4 4

04 L 0. C O 4 3

Q L 9, 4 2 0 Q 0 Q7 / 0

QοQ 9 4 2 9 7 2 4 2 9

4 τ: 0 2 4 3

4.1 9 4 2

42 2. 4 3 3

30 43 2 4 3 3

44 2.52 4 3 4

45 2.52 4 3 3

2 4 3

4.7 0 C O

DZ 4 3

¾ 48 2.52 4 3 3

4Q 2.52 3 2

0U 2.52 4 3 0

51 2.52 4 4 3

52 2.52 4 4 4

40 53 2.52 4 3 3

54 2.52 3 2 2

55 2.52 4 2 2

56 2.52 4 3 3

57 2.52 3 2 2

45 58 2.52 3 1 2

59 2.52 3 2 3

60 2.52 3 3 3 Table 6 (continued)

I-dani compound Treatment amount Herbicidal effect

No. a / a A B c

2.52 4 3 3

62 2.52 4 3 3

63 2.52 4 3 3

64 2.52 4 3 3

65 2.52 5 3 3

66 2.52 4 3 3

67 2.52 4 3 3

68 2.52 5 3 3

69 2.52 4 3 3

70 2.52 4 1 0

71 2.52 4 1 1

72 2.52 3 2 2

73 2.52 4 2 2

74 2.52 4 3 4

75 2.52 4 3 4

76 2.52 3 3 3

77 2.52 4 3 4

78 2.52 4 4 4

79 2.52 4 2 3

80 2.52 5 4 5 Table 7 Compound Treatment dose Herbicidal effect

No. g / a D E F b c

1 6.3 5 1 3 0 0

2 6.3 5 2 1 0 0

3 6.3 5 1 1 0 0

4 6.3 5 4 4 0 0

5 6.3 5 0 3 0

6 6.3 5 1 3 0

7 6.3 5 0 3 0

8 6.3 5 4 4 0

9 6.3 0 1 3 0

10 6.3 5 5 5 0

11 6.3 4 0 3 0

12 6.3 5 2 5 0 Table 7 (continued a.

Γ) E F h u. 0 4 0

0 4 o o re «re 4 5 o o in re ♦ re 2 3 o o

17 6.3 5 3 4 1 o

18 6.3 5 4 5 o o

19 6.3 5 3 4 o o

20 6.3 3 1 3 o o

15 21 6.3 5 0 2 o o

22 6 3 3 2 1 o

23 6.3 5 1 1 o

24 6.3 4 0 3 o o

25 6.3 o 0 0 o o

20 26 6.3 4 3 3 o o

27 3 4 n o lili o o 2 3

2Q 4 2 o o

u · ¾ 0 5 o Re K 2 3 o

4 5 o]

3 3 o

34 6 3 2 3 3 o 0

35 6.3 3 2 0 o

30 37 6.3 5 3 5 o

38 6.3 5 5 4 o o

39 6.3 5 2 3 1

40 6.3 5 3 3 o

41 6.3 5 0 3 0

35 42 6.3 5 4 5 0

43 6.3 5 4 4 o

44 4 5 0

45 6.3 5 4 5 0

46 6.3 4 1 4 0

40 47 6.3 5 4 5 0

48 6.3 5 3 5 0

49 6.3 5 2 5 0

50 6.3 5 5 5 0

51 6.3 5 4 5 0

45 52 6.3 2 3 4 0

53 6.3 4 1 3 1 0

54 6.3 4 1 4 0 0 Table 7 (continued)

Ί σ

You: ί! / Awe Weeding effect

ft n E F K u υ> A 3 4 1 o

ut · ¾ 20 o o

4 4 2 2 o o

58 6 3 4 0 3 o o

¾ 0 3 o o

2 4 o o

fi2 203 o o v fi V

4 4 o

vu fi t; 2 5 1

00 0 4 4 9 π

o 0.0 ς 5 4 o u o υ

a 0.04 4 1 o

nr \

iv 0.0 0 0 4 U u

71 6.3 3 0 2 0 0

72 6. 3 2 0 3 0 0

73 6.3 2 0 2 0

74 6.3 4 2 5 0 0

75 6.3 4 4 4 1 0

76 6 * 3 4 1 3 0 0

77 6.3 5 3 5 0 0

78 6.3 5 1 4 0 0

79 6.3 4 1 3 0 0

80 6. 3 4 2 3 0 0 Comparative example

Next, comparative examples of the herbicide of the compound of the present invention and the prior art will be described.

(Comparative Example 1) Herbicidal effect test by weed pretreatment under flooded conditions

After placing alluvial soil in a 1 / 100-k are no-well pot, water was added and mixed to obtain a flooding condition with a depth of 4 cm. The seeds of fireflies, oaks, and red kegweed were mixed in the above pots. The pot was placed in a greenhouse at 253 ° C, and on the third day after seeding, the compound of the present invention, N0.1, prepared according to Formulation Example 2 was brought to a prescribed dose on the water surface. The emulsion was processed by dilution with water. Similarly, the following compounds (control compounds) described in JP-A-60-148679:

Was also processed. On the 25th day after the treatment, the herbicidal effects on various weeds were investigated. 0: 5% to less than 15% wither, 1: 5% to less than 15% wither, 2: 15% to less than 30% wither, 3: 30% to less than 40% wither, 4: 40% 5% to less than 50% wither, 5: 50% to less than 60% wither, 6: 60% to less than 70% wither, 7: 70% to less than 85% wither, 8 Is a 10-point scale indicating that 85% or more and less than 95% wither, and 9 is more than 95% wither. The results are shown in Table 8. However, in the table, B represents firefly, C represents conger, and G represents swordfish.

Table 8

Compound Treatment dose Herbicidal effect

g / a B C G Compound of the present invention No. 1 0.03125 8 6 7

Compound of the present invention No. 1 0.125 8 7 7

Control compound 0.03125 0 0.1

Control compound 0.125 1 1 1

(Comparative Example 2) Chemical damage test on transplanted rice under water leakage conditions

A small hole was drilled there, and alluvial soil was placed in a 1Z1000 arel no bowel pot where water could be leaked, and then water was added and mixed, and the condition of flooding at a depth of 4 cm was established. The 2.5-leaf stage rice was transplanted there. The compound N of the present invention was prepared by placing the pot in a greenhouse at 25 to 30 ° C and cultivating the rice according to Formulation Example 2 so that a predetermined amount of the drug was brought to the surface of the water 8 days after transplantation. The 0.1 emulsion was diluted with water and processed. Similarly, The following compounds described in JP-A-8-193304 (control compound:

Was also processed. Leakage treatment was performed at 2 cm Z days for 24 days from the day after the treatment. On the 27th day after the treatment, the effects on rice were examined according to the criteria of Comparative Example 1. Table 9 shows the results. Here, a represents transplanted rice. Table 9

Compound Treatment dose

g / a Compound of the present invention N 0.0

Compound of the invention N 0.2

Control compound 8

Industrial applicability

The potato rubamoylte trazolinones of the present invention have excellent herbicidal activity and selectivity to crops, and can be used as pesticides and herbicides containing them.

Claims

Scope of claim (1)

Where L ′ represents CR ² R ³ ;

L ² represents CR ⁴ R ⁵ , CR ⁴ R ⁵ CR ⁶ R ⁷ , CR ⁴ R ⁵ CR ⁶ R ⁷ CR ⁸ R ⁹ or CR ⁴ R ⁵ C RSR'CRSITCR'OR ¹¹ ;

L'- L ² is when the ^{^{^{^{CR 2 R 3 CR 4 R 5}}}} R ', R 2, R 3, more than any one of R ⁴ and R ^5, ^ -! ^ Ji! ^! ^ Ji! ^! ^ Ji! ^! In case of ^! ^ ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ^6, and R ⁷ , and L′—L ² is CR ² R ³ CR ⁴ R ⁵ CR ⁶ R ⁷ CR ⁸ R ⁹ In the case of R ¹ R ² , R ³ , R \ R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ , L ¹ — L ² is CR ² R ³ CR ⁴ R ⁵ CR ⁶ R ⁷ CR ⁸ R ⁹ CR 'OR ¹¹ is one of R', R ² , R ³ , R \ R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ The above are phenyl groups (however, phenyl groups are the same or different substituents selected from alkyl, d-haloalkyl, _4- alkoxy, cyano, nitro and halogen atoms). . which may be Yotsute substituted), 5 heterocycle or Ji to 6-membered ₃ - ₆ cycloalkyl group were tables, others are each independently a hydrogen atom, d ₄ alkyl, C, _, Roaruki Le group, C, - ₄ alkoxy group, Shiano group, nitro port group Other represents a halogen atom, R ¹² and R ¹³ are each independently hydrogen atom, C, ₆ alkyl group, C ₃ - ₆ cycloalkyl group, C _{3 6} cycloalkenyl group, C _{2 4} alkenyl, C ₂ - ₄ alkynyl, haloalkyl groups, C _{3 6} C substituted with a cycloalkyl group, - ₂ alkyl groups, C Bok ₄ alkoxy group (wherein, R ¹² and R ¹³ simultaneously - never represents an _alkoxy group.) , C, ₄ alkoxy C alkyl group, C alkylthio C ₄ alkyl group, phenyl group (however, phenyl group Is d alkyl, C, - ₄ haloalkyl groups, C -! Alkoxy group, Shiano group, may by connexion substituted with one or more substituents the same or different selected from the two preparative port group and a halogen atom . ), Benzyl group, piperidine 1

—Yl group (However, R ¹² and R ¹³ do not represent a piperidine-11-yl group at the same time.), A pyrrolidine-11-yl group (where R ¹² and R ¹³ are simultaneously a pyrrolidine-11. ), A morpholine-l-yl group (R ¹² and R ¹³ do not represent a morpholine-l-yl group at the same time.) Or 3,6-dihydro 2 H Represents a pyran-4-yl group, provided that R ¹² and R ¹³ may form a 3- to 9-membered ring together with the nitrogen atom to which they are bonded, and an oxygen atom, sulfur Atom, a nitrogen atom which may be substituted with a C ぃ₄ alkyl group, a carbonyl group, a sulfonyl group or an unsaturated bond, and the ring may be substituted with a C ぃ₄ alkyl group. May be bridged by a C alkylene and the ring may be bridged by a benzene ring. Rather it may also have been engaged,

The 5- or 6-membered hetero ring is a thiophene ring, a furan ring, a pyrrol ring, an oxazole ring, a thiazolyl ring, an imidazole ring, an isooxazole ring, an isothiazole ring, a birazol ring, 3,4-oxadiazole ring, 1,3,4-thiadiazole ring, 1,3,4-triazole ring, 1,2,4-year-old oxadizazole ring, 1,2,4-thiadiazole ring, 1 , 2,4-triazole ring, 1,2,3-oxaziazol ring, 1,2,3-thiadiazol ring, tetrazole ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine And a 1,3,5-triazine ring or a 1,2,4-triazine ring.

2. an L ¹ and L ² are both methylene group, R ¹ is phenyl group (wherein, phenyl group C, _ ₄ alkyl group, d - Bruno, mouth alkyl group, C, - ₄ alkoxy group, Shiano group, 2. The carbamoylte trazolinones according to claim 1, which may be substituted by one or more substituents which are the same or different from each other and selected from a nitro group and a halogen atom.

3. R ¹² is an alkyl group having 1 to 4 carbon atoms, and R ¹³ is a phenyl group (provided that Le group C, - ₄ alkyl groups, C haveヽRoarukiru groups, C, - ₄ alkoxy group, Shiano group, optionally substituted by one or more substituents the same or different selected from two Toro group and a halogen atom Is also good. 2. The rubamoyl tetrazolinones according to claim 1, wherein

4. A pesticide comprising the active ingredient of the present invention as claimed in any one of claims 1 to 3 as an active ingredient.

5. A herbicide comprising the carpamoylte trazolinones according to any one of claims 1 to 3 as an active ingredient.