JP2015164899A - Pyrazole derivative, and pest control agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel pest control agent, especially an insecticide or an acaricide.SOLUTION: There is provided a pyrazole derivative and a pest control agent represented by formula (1), where Arepresents -N(O)or -CR, R, R, and Rrepresent independently hydrogen, halogen, alkyl or the like, Rrepresents hydrogen, alkyl or the like, Rrepresents -C(O) Ror the like, Ris -C(=NOR) Ror the like, Rand Rrepresent independently alkyl or the like, m1 and m2 represent independently an integer of 0 or 1, and n represents an integer of 0-3.

Description

  The present invention relates to a novel pyrazole derivative and a salt thereof, and a pest control agent containing the compound as an active ingredient. The pest control agent in the present invention is the field of agriculture and horticulture or the field of livestock and hygiene (internal parasites / external parasites for domestic animals and pets, hygiene pests and unpleasant pests for domestic and commercial use) It means a pest control agent for harmful arthropods such as The agrochemical in the present invention means an insecticide / acaricide, nematicide, herbicide, fungicide, etc. in the field of agriculture and horticulture.

  For example, although pyrazole derivatives are disclosed in Patent Documents 1 to 9, nothing is disclosed about the pyrazole derivative according to the present invention. Furthermore, its usefulness as a pest control agent, particularly an insecticide / acaricide, and an internal or ectoparasite control agent for mammals or birds is not known at all.

  Patent Document 10 discloses that pyrazole derivatives are useful as insecticides, but does not disclose any pyrazole compounds according to the present invention.

International Publication No. 2011/128304 International Publication No. 2009/076454 International Publication No. 2008/044767 US Patent Application Publication No. 2004/214838 Japanese Patent Application Publication No. 2003/313103 International Publication No. 99/010350 International Publication No. 97/034893 Japanese Patent Application Publication No. 63/174905 Japanese Patent Application Publication No. 62/153273 International Publication No. 2012/061290

  The development of pest control agents for the purpose of controlling various pests such as agricultural and horticultural pests, forest pests, and hygiene pests has progressed, and a wide variety of drugs have been put to practical use to date.

  However, due to the long-term use of such drugs, in recent years, pests have acquired drug resistance, making it difficult to control with existing insecticides and fungicides that have been used. In addition, some existing pest control agents are highly toxic, or some of them remain in the environment for a long time, and the problem of disturbing the ecosystem is becoming apparent. Under such circumstances, development of a novel pest control agent having not only high pest control activity but also low toxicity and low persistence is always expected.

  As a result of intensive studies aimed at solving the above problems, the present inventors have found that the novel pyrazole derivative represented by the following formula (1) according to the present invention has excellent pest control activity, particularly insecticide / miticide. The present invention has been completed by finding it to be an extremely useful compound that exhibits activity and has almost no adverse effects on non-target organisms such as mammals, fish and beneficial insects.

  That is, the present invention relates to the following [1] to [10].

[1]
Formula (1):

[Where A ¹ Is -N (-O) _m2 Or -CR ¹ Represents
R ¹ , R ³ And R ⁴ Each independently represents a hydrogen atom, a halogen atom, cyano, nitro, -OH, -SH, -NH ₂ , -CHO, -C (O) OH, -C (O) NH ₂ , -C (S) NH ₂ , -S (O) ₂ NH ₂ , C ₁ ~ C ₆ Alkyl, R ^28a Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, C ₃ ~ C ₈ Cycloalkyl, R ^28a Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkyl, C ₂ ~ C ₆ Alkenyl, R ^28a Optionally substituted with (C ₂ ~ C ₆ ) Alkenyl, C ₃ ~ C ₈ Cycloalkenyl, R ^28a Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkenyl, C ₂ ~ C ₆ Alkynyl, R ^28a Optionally substituted with (C ₂ ~ C ₆ ) Alkynyl, C ₁ ~ C ₆ Alkoxy, C ₁ ~ C ₆ Haloalkoxy, C ₁ ~ C ₆ Alkylthio, C ₁ ~ C ₆ Alkylsulfinyl, C ₁ ~ C ₆ Alkylsulfonyl, C ₁ ~ C ₆ Haloalkylthio, C ₁ ~ C ₆ Haloalkylsulfinyl, C ₁ ~ C ₆ Haloalkylsulfonyl, C ₁ ~ C ₆ Alkylcarbonyl, C ₃ ~ C ₈ Cycloalkylcarbonyl, C ₁ ~ C ₆ Haloalkylcarbonyl, C ₃ ~ C ₈ Halocycloalkylcarbonyl, C ₁ ~ C ₆ Alkoxycarbonyl, C ₁ ~ C ₆ Haloalkoxycarbonyl, C ₁ ~ C ₆ Alkylaminosulfonyl, di (C ₁ ~ C ₆ Alkyl) aminosulfonyl, C ₁ ~ C ₆ Alkylaminocarbonyl, di (C ₁ ~ C ₆ Alkyl) aminocarbonyl, C ₁ ~ C ₆ Alkylamino or di (C ₁ ~ C ₆ Alkyl) amino,
R ² Is a halogen atom, cyano, nitro, -OH, -SH, -NH ₂ , -CHO, -C (O) OH, -C (O) NH ₂ , -C (S) NH ₂ , -S (O) ₂ NH ₂ , C ₁ ~ C ₆ Alkyl, R ^28a Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, C ₃ ~ C ₈ Cycloalkyl, R ^28a Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkyl, C ₂ ~ C ₆ Alkenyl, R ^28a Optionally substituted with (C ₂ ~ C ₆ ) Alkenyl, C ₃ ~ C ₈ Cycloalkenyl, R ^28a Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkenyl, C ₂ ~ C ₆ Alkynyl, R ^28a Optionally substituted with (C ₂ ~ C ₆ ) Alkynyl, C ₁ ~ C ₆ Alkoxy, C ₁ ~ C ₆ Haloalkoxy, C ₁ ~ C ₆ Alkylthio, C ₁ ~ C ₆ Alkylsulfinyl, C ₁ ~ C ₆ Alkylsulfonyl, C ₁ ~ C ₆ Haloalkylthio, C ₁ ~ C ₆ Haloalkylsulfinyl, C ₁ ~ C ₆ Haloalkylsulfonyl, C ₁ ~ C ₆ Alkylcarbonyl, C ₃ ~ C ₈ Cycloalkylcarbonyl, C ₁ ~ C ₆ Haloalkylcarbonyl, C ₃ ~ C ₈ Halocycloalkylcarbonyl, C ₁ ~ C ₆ Alkoxycarbonyl, C ₁ ~ C ₆ Haloalkoxycarbonyl, C ₁ ~ C ₆ Alkylaminosulfonyl, di (C ₁ ~ C ₆ Alkyl) aminosulfonyl, C ₁ ~ C ₆ Alkylaminocarbonyl, di (C ₁ ~ C ₆ Alkyl) aminocarbonyl, C ₁ ~ C ₆ Alkylamino or di (C ₁ ~ C ₆ Alkyl) amino, and when n represents an integer of 2 or more, each R ² May be the same or different from each other,
R ^a Is a hydrogen atom, C ₁ ~ C ₆ Alkyl, R ^5a Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, C ₂ ~ C ₆ Alkenyl, R ^5a Optionally substituted with (C ₂ ~ C ₆ ) Alkenyl, C ₂ ~ C ₆ Alkynyl, R ^5a Optionally substituted with (C ₂ ~ C ₆ ) Alkynyl, -S (O) _r2 R ^6a , -C (O) OR ^6a , -C (O) SR ^6a , -C (S) OR ^6a , -C (S) SR ^6a , -C (O) R ^7a , -C (S) R ^7a , -C (O) N (R ^8a ) R ^9a Or -C (S) N (R ^8a ) R ^9a Represents
R ^b Is -C (O) R ^7b Or -C (S) R ^7b Represents
R ^5a Is a halogen atom, cyano, C ₃ ~ C ₈ Cycloalkyl, -OR ^11a , -S (O) _r2 R ^11a , -N (R ^13a ) R ^14a , -C (O) OH, -C (O) OR ^11a , -C (O) SR ^11a , -C (S) OR ^11a , -C (S) SR ^11a , -C (O) R ^12a , -C (S) R ^12a , -C (O) N (R ^13a ) R ^14a , -C (S) N (R ^13a ) R ^14a , Phenyl, (Z) _q Phenyl, naphthyl, substituted by (Z) _q Naphthyl substituted by, D1-2, D1-7, D1-8, D1-10, D1-32, D1-33, D1-34, D1-36, D1-37, D1-38, D1-79, D1-80, D1-81, D1-82, D1-84, D1-85, D1-87, D1-92, D1-93, D1-95, D1-96 or D1-98,
R ^6a Is C ₁ ~ C ₆ Alkyl or R ^10a Optionally substituted with (C ₁ ~ C ₆ ) Represents alkyl,
R ^7a Is a hydrogen atom, C ₁ ~ C ₆ Alkyl, C ₃ ~ C ₈ Cycloalkyl, R ^10a Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, -C (O) OH, -C (O) OR ^11a , -C (O) R ^12a , -C (S) R ^12a , -C (O) N (R ^13a ) R ^14a , -C (S) N (R ^13a ) R ^14a ,, -C (= NR ^13a ) R ^12a , -C (= NOH) R ^12a , -C (= NOR ^11a ) R ^12a Or -C {= NN (R ^13a ) R ^14a } R ^12a Represents
R ^7b Is -C (= NOH) R ^12b , -C (= NOR ^11b ) R ^12b Or -C {= NN (R ^13b ) R ^14b } R ^12b Represents
R ^8a Is a hydrogen atom, C ₁ ~ C ₆ Alkyl, R ^10a Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, C ₃ ~ C ₈ Cycloalkyl, R ^10a Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkyl, -OR ^11a , -S (O) _r2 R ^11a , D1-32, D1-33, D1-34 or D1-37,
R ^9a Is a hydrogen atom, C ₁ ~ C ₆ Alkyl, R ^10a Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, -S (O) _r2 R ^11a Or -C (O) R ^12a Represents
R ^10a Is a halogen atom, cyano, nitro, C ₃ ~ C ₈ Cycloalkyl, C ₃ ~ C ₈ Halocycloalkyl, —OH, —OR ^11a , -SH or -S (O) _r2 R ^11a Represents
R ^11a Is C ₁ ~ C ₆ Alkyl, R ^15a Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, C ₂ ~ C ₆ Alkenyl, R ^15a Optionally substituted with (C ₂ ~ C ₆ ) Alkenyl, C ₃ ~ C ₈ Cycloalkenyl, R ^15a Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkenyl, C ₂ ~ C ₆ Alkynyl, R ^15a Optionally substituted with (C ₂ ~ C ₆ ) Alkynyl, C ₃ ~ C ₈ Cycloalkyl, R ^15a Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkyl, -C (O) OR ^16a , -C (O) SR ^16a , -C (S) OR ^16a , -C (S) SR ^16a , -C (O) R ^17a , -C (S) R ^17a , -C (O) N (R ^18a ) R ^19a , -C (S) N (R ^18a ) R ^19a , Phenyl, (Z) _q Phenyl, naphthyl, substituted by (Z) _q Naphthyl substituted by D1-2, D1-32, D1-33, D1-34, D1-36, D1-37, D1-38, D1-79, D1-80, D1-81, D1-82, D1-84, D1-85, D1-87, D1-92, D1-93, D1-95, D1-96 or D1-98,
R ^11b Is C ₁ ~ C ₆ Alkyl, R ^15b Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, C ₂ ~ C ₆ Alkenyl, R ^15b Optionally substituted with (C ₂ ~ C ₆ ) Alkenyl, C ₃ ~ C ₈ Cycloalkenyl, R ^15b Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkenyl, C ₂ ~ C ₆ Alkynyl, R ^15b Optionally substituted with (C ₂ ~ C ₆ ) Alkynyl, C ₃ ~ C ₈ Cycloalkyl, R ^15b Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkyl, -S (O) _r3 R ^16b , -C (O) OR ^16b , -C (O) SR ^16b , -C (S) OR ^16b , -C (S) SR ^16b , -C (O) R ^17b , -C (S) R ^17b , -C (O) N (R ^18b ) R ^19b , -C (S) N (R ^18b ) R ^19b , Phenyl, (Z) _q Phenyl, naphthyl, substituted by (Z) _q Naphthyl substituted by, D1-2, D1-7, D1-8, D1-10, D1-32, D1-33, D1-34, D1-36, D1-37, D1-38, D1-79, D1-80, D1-81, D1-82, D1-84, D1-85, D1-87, D1-92, D1-93, D1-95, D1-96 or D1-98,
R ^12a Is a hydrogen atom, halogen atom, cyano, C ₁ ~ C ₆ Alkyl, R ^15a Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, C ₂ ~ C ₆ Alkenyl, R ^15a Optionally substituted (C ₂ ~ C ₆ ) Alkenyl, C ₃ ~ C ₈ Cycloalkenyl, R ^15a Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkenyl, C ₂ ~ C ₆ Alkynyl, R ^15a Optionally substituted with (C ₂ ~ C ₆ ) Alkynyl, C ₃ ~ C ₈ Cycloalkyl, R ^15a Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkyl, -OR ^16a , -S (O) _r2 R ^16a , -C (O) R ^17a , Phenyl, (Z) _q Phenyl, naphthyl, substituted by (Z) _q Naphthyl substituted by, D1-2, D1-7, D1-8, D1-10, D1-32, D1-33, D1-34, D1-36, D1-37, D1-38, D1-79, D1-80, D1-81, D1-82, D1-84, D1-85, D1-87, D1-92, D1-93, D1-95, D1-96 or D1-98,
R ^12b Is a hydrogen atom, halogen atom, cyano, C ₁ ~ C ₆ Alkyl, R ^15c Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, C ₂ ~ C ₆ Alkenyl, R ^15c Optionally substituted (C ₂ ~ C ₆ ) Alkenyl, C ₃ ~ C ₈ Cycloalkenyl, R ^15c Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkenyl, C ₂ ~ C ₆ Alkynyl, R ^15c Optionally substituted with (C ₂ ~ C ₆ ) Alkynyl, C ₃ ~ C ₈ Cycloalkyl, R ^15c Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkyl, -OR ^16c , -S (O) _r R ^16c , -C (O) OR ^16c , -C (O) SR ^16c , -C (S) OR ^16c , -C (S) SR ^16c , -C (O) R ^17c , -C (S) R ^17c , -C (O) N (R ^18c ) R ^19c , -C (S) N (R ^18c ) R ^19c , -C (= NOH) R ^17c , -C (= NOR ^16c ) R ^17c , -C {= NN (R ^18c ) R ^19c } R ^17c , Phenyl, (Z) _q Phenyl, naphthyl, substituted by (Z) _q Naphthyl substituted by, D1-2, D1-7, D1-8, D1-10, D1-32, D1-33, D1-34, D1-36, D1-37, D1-38, D1-79, D1-80, D1-81, D1-82, D1-84, D1-85, D1-87, D1-92, D1-93, D1-95, D1-96 or D1-98,
R ^13a And R ^14a Each independently represents a hydrogen atom or C ₁ ~ C ₆ Represents alkyl,
R ^13b Is a hydrogen atom, cyano, nitro, C ₁ ~ C ₆ Alkyl, R ^15b Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, C ₂ ~ C ₆ Alkenyl, R ^15b Optionally substituted with (C ₂ ~ C ₆ ) Alkenyl, C ₃ ~ C ₈ Cycloalkenyl, R ^15b Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkenyl, C ₂ ~ C ₆ Alkynyl, R ^15b Optionally substituted with (C ₂ ~ C ₆ ) Alkynyl, C ₃ ~ C ₈ Cycloalkyl, R ^15b Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkyl, -OR ^16b , -S (O) _r3 R ^16b , -C (O) OR ^16b , -C (O) SR ^16b , -C (S) OR ^16b , -C (S) SR ^16b , -C (O) R ^17b , -C (S) R ^17b , -C (O) N (R ^18b ) R ^19b , -C (S) N (R ^18b ) R ^19b , -S (O) _r3 N (R ^18b ) R ^19b , Phenyl, (Z) _q Phenyl, naphthyl, substituted by (Z) _q Naphthyl substituted by, D1-2, D1-7, D1-8, D1-10, D1-32, D1-33, D1-34, D1-36, D1-37, D1-38, D1-79, D1-80, D1-81, D1-82, D1-84, D1-85, D1-87, D1-92, D1-93, D1-95, D1-96 or D1-98 or R1- ^13b Is R ^14b Together with C ₂ ~ C ₇ An alkylene chain or C ₂ ~ C ₇ By forming an alkenylene chain of R ^13b And R ^14b May form a 3- to 8-membered ring together with the nitrogen atom to which is bonded, in which case the alkylene chain or alkenylene chain may contain one or two oxygen atoms, sulfur atoms or nitrogen atoms, and a halogen atom, cyano, Nitro, C ₁ ~ C ₆ Alkyl, R ^15b Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, C ₁ ~ C ₆ Alkoxy, C ₁ ~ C ₆ Haloalkoxy, C ₁ ~ C ₆ Alkylthio, C ₁ ~ C ₆ Haloalkylthio, C ₁ ~ C ₆ Alkylsulfinyl, C ₁ ~ C ₆ Haloalkylsulfinyl, C ₁ ~ C ₆ Alkylsulfonyl, C ₁ ~ C ₆ Haloalkylsulfonyl, phenyl, (Z) _q Optionally substituted by a phenyl, oxo group or thioxo group substituted by
R ^14b Is a hydrogen atom, cyano, nitro, C ₁ ~ C ₆ Alkyl, R ^15d Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, C ₂ ~ C ₆ Alkenyl, R ^15d Optionally substituted with (C ₂ ~ C ₆ ) Alkenyl, C ₃ ~ C ₈ Cycloalkenyl, R ^15d Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkenyl, C ₂ ~ C ₆ Alkynyl, R ^15d Optionally substituted with (C ₂ ~ C ₆ ) Alkynyl, C ₃ ~ C ₈ Cycloalkyl, R ^15d Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkyl, -OR ^16d , -S (O) _r3 R ^16d , -C (O) OR ^16d , -C (O) SR ^16d , -C (S) OR ^16d , -C (S) SR ^16d , -C (O) R ^17d , -C (S) R ^17d , -C (O) N (R ^18d ) R ^19d , -C (S) N (R ^18d ) R ^19d , -S (O) _r3 N (R ^18d ) R ^19d , Phenyl, (Z) _q Phenyl, naphthyl, substituted by (Z) _q Naphthyl substituted by, D1-2, D1-7, D1-8, D1-10, D1-32, D1-33, D1-34, D1-36, D1-37, D1-38, D1-79, D1-80, D1-81, D1-82, D1-84, D1-85, D1-87, D1-92, D1-93, D1-95, D1-96 or D1-98 or R1- ^14b Is R ^13b Together with = C (R ^14e ) R ^14f May form,
R ^14e And R ^14f Each independently represents a hydrogen atom, cyano, nitro, C ₁ ~ C ₆ Alkyl, R ^15b Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, C ₂ ~ C ₆ Alkenyl, R ^15b Optionally substituted with (C ₂ ~ C ₆ ) Alkenyl, C ₃ ~ C ₈ Cycloalkenyl, R ^15b Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkenyl, C ₂ ~ C ₆ Alkynyl, R ^15b Optionally substituted with (C ₂ ~ C ₆ ) Alkynyl, C ₃ ~ C ₈ Cycloalkyl, R ^15b Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkyl, -OR ^16b , -S (O) _r3 R ^16b , -C (O) OR ^16b , -C (O) SR ^16b , -C (S) OR ^16b , -C (S) SR ^16b , -C (O) R ^17b , -C (S) R ^17b , -C (O) N (R ^18b ) R ^19b , -C (S) N (R ^18b ) R ^19b , -S (O) _r3 N (R ^18b ) R ^19b , Phenyl, (Z) _q Phenyl, naphthyl, substituted by (Z) _q Naphthyl substituted by, D1-2, D1-7, D1-8, D1-10, D1-32, D1-33, D1-34, D1-36, D1-37, D1-38, D1-79, D1-80, D1-81, D1-82, D1-84, D1-85, D1-87, D1-92, D1-93, D1-95, D1-96 or D1-98 or R1- ^14e Is R ^14f Together with C ₂ ~ C ₇ An alkylene chain or C ₂ ~ C ₇ By forming an alkenylene chain of R ^14e And R ^14f May form a 3- to 8-membered ring together with the carbon atom to which is bonded, in which case the alkylene chain or alkenylene chain may contain 1, 2 or 3 oxygen atoms, sulfur atoms or nitrogen atoms, and a halogen atom, Cyano, nitro, C ₁ ~ C ₆ Alkyl, R ^15b Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, C ₁ ~ C ₆ Alkoxy, C ₁ ~ C ₆ Haloalkoxy, C ₁ ~ C ₆ Alkylthio, C ₁ ~ C ₆ Haloalkylthio, C ₁ ~ C ₆ Alkylsulfinyl, C ₁ ~ C ₆ Haloalkylsulfinyl, C ₁ ~ C ₆ Alkylsulfonyl, C ₁ ~ C ₆ Haloalkylsulfonyl, phenyl, (Z) _q Optionally substituted by a phenyl, oxo group or thioxo group substituted by
R ^15a Is a halogen atom, cyano, nitro, C ₃ ~ C ₈ Cycloalkyl, C ₃ ~ C ₈ Halocycloalkyl, —OH, —OR ^16a , -SH, -S (O) _r2 R ^16a , -S (= NR ^18a ) R ^16a , -S (O) (= NR ^18a ) R ^16a , Phenyl, (Z) _q Phenyl, naphthyl, substituted by (Z) _q Naphthyl substituted by, D1-2, D1-7, D1-8, D1-10, D1-32, D1-33, D1-34, D1-36, D1-37, D1-38, D1-79, D1-80, D1-81, D1-82, D1-84, D1-85, D1-87, D1-92, D1-93, D1-95, D1-96, D1-98 or -Si (R ^40a ) (R ^40b ) R ⁴⁰ Represents
R ^15b Is a halogen atom, cyano, nitro, C ₃ ~ C ₈ Cycloalkyl, C ₃ ~ C ₈ Halocycloalkyl, —OH, —OR ^16b , -SH, -S (O) _r3 R ^16b , -S (= NR ^18b ) R ^16b , -S (O) (= NR ^18b ) R ^16b , -C (O) OH, -C (O) OR ^16b , -C (O) R ^17b , -C (O) N (R ^18b ) R ^19b , Phenyl, (Z) _q Phenyl, naphthyl, substituted by (Z) _q Naphthyl substituted by, D1-2, D1-7, D1-8, D1-10, D1-32, D1-33, D1-34, D1-36, D1-37, D1-38, D1-79, D1-80, D1-81, D1-82, D1-84, D1-85, D1-87, D1-92, D1-93, D1-95, D1-96, D1-98 or -Si (R ^40a ) (R ^40b ) R ⁴⁰ Represents
R ^15c Is a halogen atom, cyano, nitro, C ₃ ~ C ₈ Cycloalkyl, C ₃ ~ C ₈ Halocycloalkyl, —OH, —OR ^16c , -SH, -S (O) _r R ^16c , -S (= NR ^18c ) R ^16c , -S (O) (= NR ^18c ) R ^16c , Phenyl, (Z) _q Phenyl, naphthyl, substituted by (Z) _q Naphthyl substituted by, D1-2, D1-7, D1-8, D1-10, D1-32, D1-33, D1-34, D1-36, D1-37, D1-38, D1-79, D1-80, D1-81, D1-82, D1-84, D1-85, D1-87, D1-92, D1-93, D1-95, D1-96, D1-98 or -Si (R ^40a ) (R ^40b ) R ⁴⁰ Represents
R ^15d Is a halogen atom, cyano, nitro, C ₃ ~ C ₈ Cycloalkyl, C ₃ ~ C ₈ Halocycloalkyl, —OH, —OR ^16d , -SH, -S (O) _r3 R ^16d , -S (= NR ^18d ) R ^16d , -S (O) (= NR ^18d ) R ^16d , Phenyl, (Z) _q Phenyl, naphthyl, substituted by (Z) _q Naphthyl substituted by, D1-2, D1-7, D1-8, D1-10, D1-32, D1-33, D1-34, D1-36, D1-37, D1-38, D1-79, D1-80, D1-81, D1-82, D1-84, D1-85, D1-87, D1-92, D1-93, D1-95, D1-96, D1-98 or -Si (R ^40a ) (R ^40b ) R ⁴⁰ Represents
R ^16a , R ^16b And R ^16d Are each independently C ₁ ~ C ₆ Alkyl, C ₂ ~ C ₆ Alkenyl, C ₂ ~ C ₆ Alkynyl, C ₃ ~ C ₈ Cycloalkyl, C ₃ ~ C ₈ Cycloalkenyl, R ²⁰ Optionally substituted with (C ₁ ~ C ₆ ) Alkyl or -C (O) R ²² Represents
R ^16c Is cyano, C ₁ ~ C ₆ Alkyl, C ₂ ~ C ₆ Alkenyl, C ₂ ~ C ₆ Alkynyl, C ₃ ~ C ₈ Cycloalkyl, C ₃ ~ C ₈ Cycloalkenyl, R ²⁰ Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, R ²⁰ Optionally substituted with (C ₂ ~ C ₆ ) Alkenyl, R ²⁰ Optionally substituted with (C ₂ ~ C ₆ ) Alkynyl, R ²⁰ Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkyl, R ²⁰ Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkenyl, -S (O) _r R ²¹ , -C (O) R ²² , Phenyl, (Z) _q Phenyl, naphthyl, substituted by (Z) _q Naphthyl substituted by, D1-2, D1-7, D1-8, D1-10, D1-32, D1-33, D1-34, D1-36, D1-37, D1-38, D1-79, D1-80, D1-81, D1-82, D1-84, D1-85, D1-87, D1-92, D1-93, D1-95, D1-96 or D1-98,
R ^17a , R ^17b , R ^17c And R ^17d Are each independently a hydrogen atom, C ₁ ~ C ₆ Alkyl, C ₂ ~ C ₆ Alkenyl, C ₂ ~ C ₆ Alkynyl, C ₃ ~ C ₈ Cycloalkyl, C ₃ ~ C ₈ Cycloalkenyl, R ²⁰ Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, R ²⁰ Optionally substituted with (C ₂ ~ C ₆ ) Alkenyl, R ²⁰ Optionally substituted with (C ₂ ~ C ₆ ) Alkynyl, R ²⁰ Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkyl, R ²⁰ Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkenyl, phenyl, (Z) _q Phenyl, naphthyl, substituted by (Z) _q Naphthyl substituted by, D1-2, D1-7, D1-8, D1-10, D1-32, D1-33, D1-34, D1-36, D1-37, D1-38, D1-79, D1-80, D1-81, D1-82, D1-84, D1-85, D1-87, D1-92, D1-93, D1-95, D1-96 or D1-98,
R ^18a And R ^19a Each independently represents a hydrogen atom, cyano or C ₁ ~ C ₆ Represents alkyl,
R ^18b , R ^19b , R ^18d And R ^19d Are each independently a hydrogen atom, cyano, C ₁ ~ C ₆ Alkyl, C ₂ ~ C ₆ Alkenyl, C ₂ ~ C ₆ Alkynyl, C ₃ ~ C ₈ Cycloalkyl, C ₃ ~ C ₈ Cycloalkenyl, R ²⁰ Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, R ²⁰ Optionally substituted with (C ₂ ~ C ₆ ) Alkenyl, R ²⁰ Optionally substituted with (C ₂ ~ C ₆ ) Alkynyl, R ²⁰ Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkyl, R ²⁰ Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkenyl, phenyl, (Z) _q Phenyl, naphthyl, substituted by (Z) _q Naphthyl substituted by, D1-2, D1-7, D1-8, D1-10, D1-32, D1-33, D1-34, D1-36, D1-37, D1-38, D1-79, D1-80, D1-81, D1-82, D1-84, D1-85, D1-87, D1-92, D1-93, D1-95, D1-96 or D1-98 or R1- ^18b Is R ^19b Together with C ₂ ~ C ₇ An alkylene chain or C ₂ ~ C ₇ By forming an alkenylene chain of R ^18b And R ^19b May form a 3- to 8-membered ring together with the nitrogen atom to which is bonded, in which case the alkylene chain or alkenylene chain may contain one or two oxygen atoms, sulfur atoms or nitrogen atoms, and a halogen atom, cyano, Nitro, C ₁ ~ C ₆ Alkyl, R ²⁰ Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, C ₁ ~ C ₆ Alkoxy, C ₁ ~ C ₆ Haloalkoxy, C ₁ ~ C ₆ Alkylthio, C ₁ ~ C ₆ Haloalkylthio, C ₁ ~ C ₆ Alkylsulfinyl, C ₁ ~ C ₆ Haloalkylsulfinyl, C ₁ ~ C ₆ Alkylsulfonyl, C ₁ ~ C ₆ Haloalkylsulfonyl, phenyl, (Z) _q Optionally substituted by a phenyl, oxo group or thioxo group substituted by
R ^18c And R ^19c Are each independently a hydrogen atom, cyano, C ₁ ~ C ₆ Alkyl, R ²⁰ Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, -OR ²¹ , -S (O) _r R ²¹ , -C (O) OR ²¹ , -C (O) R ²² , -C (S) R ²² , Phenyl or (Z) _q Represents phenyl substituted by
R ²⁰ Is a halogen atom, cyano, nitro, C ₃ ~ C ₈ Cycloalkyl, C ₃ ~ C ₈ Cycloalkenyl, C ₁ ~ C ₆ Alkoxy, C ₁ ~ C ₆ Alkylthio, C ₁ ~ C ₆ Alkylsulfinyl, C ₁ ~ C ₆ Alkylsulfonyl, -C (O) OR ²¹ , Phenyl or (Z) _q Represents phenyl substituted by
R ²¹ And R ²² Are each independently C ₁ ~ C ₆ Alkyl, C ₁ ~ C ₆ Haloalkyl, phenyl or (Z) _q Represents phenyl substituted by
D1-2, D1-7, D1-8, D1-10, D1-32, D1-33, D1-34, D1-36, D1-37, D1-38, D1-51, D1-79, D1- 80, D1-81, D1-82, D1-84, D1-85, D1-87, D1-92, D1-93, D1-95, D1-96 and D1-98 are represented by the following structures, respectively. Represents the ring

X ¹ and X ^1b are each independently a halogen atom, cyano, nitro, —OH, —SH, —NH ₂ , —CHO, —C (O) OH, —C (O) NH ₂ , —C (S _{) NH 2, -S (O)} 2 NH 2, C 1 ~C 6 ^alkyl, optionally substituted with ^{R 28} _(C 1 ~C _{6) alkyl,} C 2 -C _{6 alkenyl,} C 2 -C ₆ alkynyl , _C 3 -C _{8 cycloalkyl,} C 2 -C _{6 haloalkenyl,} C 2 -C _{6 haloalkynyl,} C 3 -C _{8 halocycloalkyl,} C 1 -C _{6 alkoxy,} C 1 -C ₆ haloalkoxy, C ₁ -C _{6 alkylthio,} C 1 -C _{6 haloalkylthio,} C 1 -C _{6 alkylsulfinyl,} C 1 -C _{6 haloalkylsulfinyl,} C 1 -C _{6 alkylsulfonyl,} C 1 -C ₆ haloalkylsulfonyl, _{C 1} C _{6 alkylcarbonyl,} C 3 -C _{8 cycloalkylcarbonyl,} C 1 -C _{6 haloalkylcarbonyl,} C 3 -C ₈ halocycloalkyl _carbonyl, C 1 -C _{6 alkoxycarbonyl,} C 1 -C ₆ haloalkoxycarbonyl, C ₁ -C ₆ alkylaminosulfonyl, di _(C 1 -C ₆ alkyl) _{aminosulfonyl,} C 1 -C ₆ alkylaminocarbonyl, di _(C 1 -C ₆ alkyl) _{aminocarbonyl,} C 1 -C ₆ alkylamino or di _(C 1 -C ₆ alkyl) an amino, g1, when g2 or g4 represents an integer of 2 or more, each ^{X 1} may be also or different from each other the same as each other, or, f4, f5 when f7 or the f9 represents an integer of 2 or more, each X ^1b is also even or different from each other the same as each other Further, when two ^{which X 1b} are substituted on the same carbon, the two ^{X 1b} oxo together, thioxo, _imino, C 1 -C _{6 alkylimino,} C 1 -C ₆ alkoxyimino or C ₁ -C ₆ alkylidene may be formed,
X ^1a is a hydrogen atom, cyano, —OH, —NH ₂ , —CHO, —C (O) NH ₂ , —C (S) NH ₂ , —S (O) ₂ NH ₂ , C _{1 to} C ₆ alkyl. , _C 2 -C _{6 alkenyl,} C 2 -C _{6 alkynyl,} C 3 -C ₈ ^cycloalkyl, optionally substituted with ^{R 28} _(C 1 ~C ₆₎ ^alkyl, optionally substituted with ^{R 28} (C ₂ -C ₆₎ ^alkenyl, optionally substituted with ^{R 28} _(C 2 ~C ₆₎ ^alkynyl, optionally substituted with ^{R 28} _(C 3 ~C ₈₎ ^cycloalkyl, optionally substituted with ^{R 28} (C ₃ -C ₈ ) cycloalkenyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ alkylsulfonyl, C ₁ ~C ₆ haloalkylthio, ₁ -C _{6 haloalkylsulfinyl,} C 1 -C _{6 haloalkylsulfonyl,} C 1 -C _{6 alkylcarbonyl,} C 3 -C _{8 cycloalkylcarbonyl,} C 1 -C _{6 haloalkylcarbonyl,} C 3 -C ₈ halocycloalkyl carbonyl, C ₁ -C ₆ alkoxycarbonyl, C ₁ -C ₆ haloalkoxycarbonyl, C ₁ -C ₆ alkylaminosulfonyl, di (C ₁ -C ₆ alkyl) aminosulfonyl, C ₁ -C ₆ alkylaminocarbonyl, di (C ₁ -C ₆ alkyl) _{aminocarbonyl-substituted,} C 1 -C ₆ alkylamino, di _(C 1 -C ₆ alkyl) amino, _phenyl, optionally optionally substituted phenyl or a halogen atom at C 1 -C ₆ alkyl Represented phenyl,
Z is a halogen atom, cyano, nitro, —OH, —SH, —NH ₂ , —CHO, —C (O) OH, —C (O) NH ₂ , —C (S) NH ₂ , —S (O ) ₂ NH ₂ , C ₁ -C ₆ alkyl, (C ₁ -C ₆ ) alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₈ cycloalkyl optionally substituted with R ²⁸ C ₂ -C ₆ haloalkenyl, C ₂ -C ₆ haloalkynyl, C ₃ -C ₈ halocycloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ alkylthio, C ₁ -C _{6 haloalkylthio,} C 1 -C _{6 alkylsulfinyl,} C 1 -C _{6 haloalkylsulfinyl,} C 1 -C _{6 alkylsulfonyl,} C 1 -C _{6 haloalkylsulfonyl,} C 1 -C ₆ alkylcarbonyl, C ₃ -C _{8 cycloalkylcarbonyl,} C 1 -C _{6 haloalkylcarbonyl,} C 3 -C ₈ halocycloalkyl _carbonyl, C 1 -C _{6 alkoxycarbonyl,} C 1 -C _{6 haloalkoxycarbonyl,} C 1 -C ₆ alkyl Aminosulfonyl, di (C ₁ -C ₆ alkyl) aminosulfonyl, C ₁ -C ₆ alkylaminocarbonyl, di (C ₁ -C ₆ alkyl) aminocarbonyl, C ₁ -C ₆ alkylamino or di (C ₁ -C ₆ alkyl) amino, and when q represents an integer of 2 or more, each Z may be the same as or different from each other,
R ²⁸ and R ^28a are each independently a halogen atom, —OH, —SH, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfonyl or C ₁ -C ₆ haloalkylsulfonyl,
R ⁴⁰ , R ^40a and R ^40b each independently represent C ₁ -C ₆ alkyl;
g1 and n each independently represent an integer of 0, 1, 2, or 3;
g2 represents an integer of 0, 1 or 2;
g4 and f4 each independently represent an integer of 0, 1, 2, 3 or 4;
f5 represents an integer of 0, 1, 2, 3, 4 or 5,
f7 represents an integer of 0, 1, 2, 3, 4, 5, 6 or 7,
f9 represents an integer of 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9,
q represents an integer of 1, 2, 3, 4 or 5;
m1, m2 and m3 each independently represent an integer of 0 or 1,
r, r2 and r3 each independently represents an integer of 0, 1 or 2. ] The pyrazole derivative represented by these, or its salt.

[2]
A ¹ represents -CR ¹
R ¹ , R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom or C ₁ -C ₆ alkyl;
R ² represents a pyrazole derivative or a salt thereof according to the above [1], wherein R ² represents a halogen atom or C ₁ -C ₆ alkyl.

[3]
A ¹ represents -N (-O) _m2 ,
R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom or C ₁ -C ₆ alkyl;
R ² represents a pyrazole derivative or a salt thereof according to the above [1], wherein R ² represents a halogen atom or C ₁ -C ₆ alkyl.

[4]
R ¹ represents a hydrogen atom or a halogen atom,
R ⁴ represents a hydrogen atom,
R ³ represents a hydrogen atom, a halogen atom or C ₁ -C ₆ alkyl,
R ^a is a hydrogen atom, C ₁ -C ₆ alkyl, (C ₁ -C ₆ ) alkyl optionally substituted with R ^5a , C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, -S (O) _r2 R ^6a, represents ^{-C (O) oR 6a, -C} (O) R 7a, -C (O) N (R 8a) R 9a or ^{-C (S) N (R 8a} ) R 9a,
R ^5a is cyano, C ₃ -C ₈ cycloalkyl, —OR ^11a , —S (O) _{r 2} R ^11a , —C (O) OH, —C (O) OR ^11a , —C (O) N (R ^13a ) represents R ^14a , phenyl, phenyl substituted by (Z) _q , D1-32, D1-33 or D1-34;
R ^6a represents C ₁ -C ₆ alkyl;
R ^7a represents C ₃ -C ₈ cycloalkyl, (C ₁ -C ₆ ) alkyl optionally substituted with R ^10a or —C (═NOR ^11a ) R ^12a ,
R ^8a represents a hydrogen atom or C ₁ -C ₆ alkyl;
R ^9a represents a hydrogen atom or C ₁ -C ₆ alkyl,
R ^10a represents —S (O) _r2 R ^11a ,
R ^11a is C ₁ -C ₆ alkyl, (C ₁ -C ₆ ) alkyl optionally substituted with R ^15a , C ₂ -C ₆ alkynyl, -C (O) OR ^16a , -C (O) R ^17a Or -C (O) N (R ^18a ) R ^19a
R ^11b represents C ₁ -C ₆ alkyl, (C ₁ -C ₆ ) alkyl optionally substituted with R ^15b , —C (O) OR ^16b or —C (O) R ^17b ,
R ^12a represents (C ₁ -C ₆ ) alkyl optionally substituted with R ^15a ,
R ^12b is a hydrogen atom, _cyano, C 1 -C ₆ ^alkyl, optionally substituted with ^{R 15c} _(C 1 ~C ₆₎ ^alkyl, optionally substituted with ^{R 15c} _(C 2 ~C ₆₎ alkenyl, optionally substituted with R ^15c _(C 3 ~C _{8) ^{cycloalkyl, -S (O) r R 16c}} , -C (O) R 17c, phenyl, phenyl substituted by _{(Z) q,} D1-2 , D1-32 or D1-34,
R ^13b is a hydrogen atom, C ₁ -C ₆ alkyl, (C ₁ -C ₆ ) alkyl optionally substituted with R ^15b , C ₂ -C ₆ alkenyl, —S (O) _r 3 R ^16b , —C ( O) OR ^16b , —C (O) R ^17b , —C (O) N (R ^18b ) R ^19b , phenyl or D1-37,
R ^14b represents a hydrogen atom,
R ^15a represents —OR ^16a , —S (O) _{r 2} R ^16a , phenyl or —Si (R ^40a ) (R ^40b ) R ⁴⁰ ,
R ^15b is a halogen atom, cyano, C ₃ -C ₈ cycloalkyl, —OR ^16b , —S (O) _r 3 R ^16b , —C (O) OR ^16b or —C (O) N (R ^18b ) R ^19b. Represents
R ^15c represents a halogen atom, —OR ^16c , —S (O) _r R ^16c or D 1-7;
R ^16a represents C ₁ -C ₆ alkyl or (C ₁ -C ₆ ) alkyl optionally substituted with R ²⁰ ;
R ^16b represents C ₁ -C ₆ alkyl or (C ₁ -C ₆ ) alkyl optionally substituted with R ²⁰ ;
R ^16c represents C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, (C ₁ -C ₆ ) alkyl optionally substituted with R ²⁰ , —S (O) _r R ²¹ or D1-32,
R ^17a represents C ₁ -C ₆ alkyl or phenyl;
R ^17b represents a hydrogen atom, C ₁ -C ₆ alkyl, C ₃ -C ₈ cycloalkyl or (C ₁ -C ₆ ) alkyl optionally substituted with R ²⁰ ,
R ^17c represents C ₁ -C ₆ alkyl;
R ^18a and R ^19a each independently represent C ₁ -C ₆ alkyl;
R ^18b represents a hydrogen atom or phenyl substituted by (Z) _q ;
R ^19b represents a hydrogen atom or (C ₁ -C ₆ ) alkyl optionally substituted with R ²⁰ ,
R ²⁰ represents a halogen atom, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio or phenyl,
R ²¹ represents phenyl substituted by (Z) _q ;
X ¹ represents (C ₁ -C ₆ ) alkyl optionally substituted with R ²⁸ ,
R ²⁸ represents a halogen atom,
Z represents a halogen atom or a _C 1 -C ₆ alkyl,
g1 and g4 each independently represent an integer of 0 or 1,
m1, m3 and n represent 0;
q represents an integer of 1 or 2,
r and r3 each independently represents an integer of 0, 1 or 2;
The pyrazole derivative or the salt thereof according to the above [2], wherein r2 represents 0 or an integer of 2.

[5]
A pest control agent containing one or more selected from the pyrazole derivatives described in the above [1] to [4] and salts thereof as an active ingredient.

[6]
An agrochemical containing one or more selected from the pyrazole derivatives according to the above [1] to [4] and salts thereof as an active ingredient.

[7]
A mammal or bird internal or ectoparasite control agent comprising one or more selected from the pyrazole derivatives described in the above [1] to [4] and salts thereof as an active ingredient.

[8]
An insecticide or acaricide containing as an active ingredient one or more selected from the pyrazole derivatives described in [1] to [4] above and salts thereof.

[9]
The soil treatment agent which contains 1 type, or 2 or more types chosen from the pyrazole derivative and its salt of said [1]-[4] as an active ingredient.

[10]
The soil treatment agent according to the above [9], wherein the soil treatment method is soil irrigation treatment.

  The compound of the present invention has excellent insecticidal / miticidal activity against many agricultural pests, spider mites, mammals or birds, or against insects that have acquired resistance to existing insecticides. Even against this, it exhibits a sufficient control effect. Furthermore, it has little adverse effect on mammals, fish and beneficial insects, has low persistence, and has a light environmental impact.

  Therefore, the present invention can provide a useful novel pest control agent.

  The compounds included in the present invention may have geometrical isomers of E-form and Z-form depending on the type of substituent, and the present invention is not limited to these E-form, Z-form or E-form. And a mixture containing the Z-form in an arbitrary ratio. In addition, the compounds included in the present invention include optically active substances resulting from the presence of one or more asymmetric carbon atoms, but the present invention includes all optically active substances or racemates.

  Among the compounds included in the present invention, those that can be converted into acid addition salts according to a conventional method include, for example, hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, and the like. Salts of inorganic acids such as salts, nitric acid, sulfuric acid, phosphoric acid, chloric acid, perchloric acid, salts of sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, Salts of carboxylic acids such as formic acid, acetic acid, propionic acid, trifluoroacetic acid, fumaric acid, tartaric acid, succinic acid, maleic acid, malic acid, succinic acid, benzoic acid, mandelic acid, ascorbic acid, lactic acid, gluconic acid, citric acid, etc. A salt of an amino acid such as glutamic acid or aspartic acid can be used.

  Alternatively, among the compounds included in the present invention, those that can be converted into metal salts according to conventional methods include, for example, alkali metal salts such as lithium, sodium, and potassium, and alkaline earth metals such as calcium, barium, and magnesium. It can be a salt or a salt of aluminum.

  Next, specific examples of each substituent shown in the present specification are shown below. Here, n- represents normal, i- represents iso, s- represents secondary, and tert- represents tertiary, and Ph represents phenyl.

  Examples of the halogen atom in the present specification include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. In the present specification, the notation “halo” also represents these halogen atoms.

The notation of C _a -C _b alkyl in the present specification represents a linear or branched hydrocarbon group having a carbon number of _a to _b , for example, methyl group, ethyl group, n-propyl group, Specific examples include i-propyl group, n-butyl group, i-butyl group, s-butyl group, tert-butyl group, n-pentyl group, 1,1-dimethylpropyl group, n-hexyl group, and the like. Each selected range of carbon atoms is selected.

In the present specification, C _a -C _b haloalkyl is represented by a linear or branched chain having _a to _b carbon atoms in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom. Represents a hydrocarbon group, and when substituted by two or more halogen atoms, the halogen atoms may be the same as or different from each other. For example, fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, difluoromethyl group, dichloromethyl group, trifluoromethyl group, chlorodifluoromethyl group, trichloromethyl group, bromodifluoromethyl group, 2-fluoroethyl group, 2- Chloroethyl group, 2-bromoethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 2-chloro-2,2-difluoroethyl group, 2,2,2-trichloroethyl group, 1 , 1,2,2-tetrafluoroethyl group, 2-chloro-1,1,2-trifluoroethyl group, pentafluoroethyl group, 3,3,3-trifluoropropyl group, 2,2,3,3 , 3-pentafluoropropyl group, 1,1,2,3,3,3-hexafluoropropyl group, heptafluoropropyl group 2,2,2-trifluoro-1- (trifluoromethyl) ethyl group, 1,2,2,2-tetrafluoro-1- (trifluoromethyl) ethyl group, 2,2,3,3,4, Specific examples include 4,4-heptafluorobutyl group, nonafluorobutyl group and the like, and each is selected within the range of the number of carbon atoms designated.

In the present specification, C _a -C _b cycloalkyl represents a cyclic hydrocarbon group having a carbon number of _a to _b , and forms a monocyclic or complex ring structure having 3 to 6 members. I can do it. Each ring may be optionally substituted with an alkyl group within the range of the specified number of carbon atoms. Specific examples include, for example, cyclopropyl group, 1-methylcyclopropyl group, 2-methylcyclopropyl group, 2,2-dimethylcyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like. Selected in a range of numbers.

In the present specification, C _a -C _b alkenyl is a linear or branched chain composed of _a to _b carbon atoms and has one or more double bonds in the molecule. Represents a saturated hydrocarbon group, for example, vinyl group, 1-propenyl group, 2-propenyl group, 1-methylethenyl group, 2-butenyl group, 2-methyl-2-propenyl group, 3-methyl-2-butenyl group, 1 , 1-dimethyl-2-propenyl group and the like are listed as specific examples, and each is selected within the range of the designated number of carbon atoms.

In the present specification, C _a -C _b haloalkenyl is a linear or branched chain in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom, and the number of carbon atoms is ab. And an unsaturated hydrocarbon group having one or more double bonds in the molecule. At this time, when substituted by two or more halogen atoms, these halogen atoms may be the same as or different from each other. For example, 2,2-dichlorovinyl group, 2-fluoro-2-propenyl group, 2-chloro-2-propenyl group, 3-chloro-2-propenyl group, 2-bromo-2-propenyl group, 3,3-difluoro -2-propenyl group, 2,3-dichloro-2-propenyl group, 3,3-dichloro-2-propenyl group, 2,3,3-trifluoro-2-propenyl group, 2,3,3-trichloro- 2-propenyl group, 1- (trifluoromethyl) ethenyl group, 4,4-difluoro-3-butenyl group, 3,4,4-trifluoro-3-butenyl group, 3-chloro-4,4,4- Specific examples include a trifluoro-2-butenyl group and the like, and each is selected within the range of the designated number of carbon atoms.

The notation of C _a -C _b cycloalkenyl in the present specification represents a cyclic unsaturated hydrocarbon group having 1 to 2 carbon atoms and having 1 or 2 or more double bonds. A monocyclic or complex ring structure from a member ring to a 6-member ring can be formed. Each ring may be optionally substituted with an alkyl group within the range of the specified number of carbon atoms, and the double bond may be either endo- or exo-. Specific examples include 1-cyclopenten-1-yl group, 2-cyclopenten-1-yl group, 1-cyclohexen-1-yl group, 2-cyclohexen-1-yl group, and the like. Selected in a range of numbers.

In the present specification, C _a -C _b alkylidene represents a linear or branched hydrocarbon group having a carbon number of _a to _b and bonded by a double bond, such as a methylidene group or an ethylidene group. Specific examples include a group, a propylidene group, a 1-methylethylidene group, and the like, and each group is selected within the range of the designated number of carbon atoms.

In the present specification, C _a -C _b alkynyl is a linear or branched chain composed of _a to _b carbon atoms and has one or more triple bonds in the molecule. Represents a hydrocarbon group, for example, ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1,1-dimethyl-2-propynyl group, etc. Each of which is selected for each specified number of carbon atoms.

In the present specification, C _a -C _b haloalkynyl represents a linear or branched chain in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom, and the number of carbon atoms is a to b. And an unsaturated hydrocarbon group having one or more triple bonds in the molecule. At this time, when substituted by two or more halogen atoms, these halogen atoms may be the same as or different from each other. Specific examples include 2-chloroethynyl group, 2-bromoethynyl group, 2-iodoethynyl group, 3-chloro-2-propynyl group, 3-bromo-2-propynyl group, 3-iodo-2-propynyl group and the like. Each of which is selected for each specified number of carbon atoms.

The notation of C _a -C _b alkoxy in the present specification represents an alkyl-O— group having the above-mentioned meaning consisting of _a to _b carbon atoms, for example, methoxy group, ethoxy group, n-propyloxy group, Specific examples include an i-propyloxy group, an n-butyloxy group, an i-butyloxy group, an s-butyloxy group, a tert-butyloxy group, and the like, and each is selected within the range of the designated number of carbon atoms.

The notation of C _a -C _b haloalkoxy in the present specification represents a haloalkyl-O— group having the above-mentioned meaning consisting of _a to _b carbon atoms, for example, difluoromethoxy group, trifluoromethoxy group, chlorodifluoro Methoxy group, bromodifluoromethoxy group, 2-fluoroethoxy group, 2-chloroethoxy group, 2,2,2-trifluoroethoxy group, 1,1,2,2, -tetrafluoroethoxy group, 2-chloro-1 Specific examples include 1,2,2-trifluoroethoxy group, 1,1,2,3,3,3-hexafluoropropyloxy group and the like, and each is selected within the range of the designated number of carbon atoms.

The notation of C _a -C _b alkylthio in the present specification represents an alkyl-S-group having the above-mentioned meaning consisting of _a to _b carbon atoms, for example, methylthio group, ethylthio group, n-propylthio group, i Specific examples include -propylthio group, n-butylthio group, i-butylthio group, s-butylthio group, tert-butylthio group and the like, which are selected within the range of the number of carbon atoms specified.

The notation of C _a -C _b haloalkylthio in the present specification represents a haloalkyl-S— group having the above-mentioned meaning consisting of _a to _b carbon atoms, for example, difluoromethylthio group, trifluoromethylthio group, chlorodifluoro Methylthio group, bromodifluoromethylthio group, 2,2,2-trifluoroethylthio group, 1,1,2,2-tetrafluoroethylthio group, 2-chloro-1,1,2-trifluoroethylthio group, Pentafluoroethylthio group, 1,1,2,3,3,3-hexafluoropropylthio group, heptafluoropropylthio group, 1,2,2,2-tetrafluoro-1- (trifluoromethyl) ethylthio group , Nonafluorobutylthio group and the like are given as specific examples, and each is selected within the range of the designated number of carbon atoms.

The notation of C _a -C _b alkylsulfinyl in the present specification represents an alkyl-S (O) -group having the above-mentioned meaning consisting of _a to _b carbon atoms, for example, methylsulfinyl group, ethylsulfinyl group, Specific examples include n-propylsulfinyl group, i-propylsulfinyl group, n-butylsulfinyl group, i-butylsulfinyl group, s-butylsulfinyl group, tert-butylsulfinyl group and the like. The range is selected.

In the present specification, the expression C _a -C _b haloalkylsulfinyl represents a haloalkyl-S (O) -group having the above-mentioned meaning consisting of _a to _b carbon atoms, for example, difluoromethylsulfinyl group, trifluoromethyl Sulfinyl group, chlorodifluoromethylsulfinyl group, bromodifluoromethylsulfinyl group, 2,2,2-trifluoroethylsulfinyl group, 1,2,2,2-tetrafluoro-1- (trifluoromethyl) ethylsulfinyl group, nona Specific examples include a fluorobutylsulfinyl group and the like, and each is selected within the range of the designated number of carbon atoms.

The notation of C _a -C _b alkylsulfonyl in the present specification represents an alkyl-SO ₂ -group having the above-mentioned meaning consisting of _a to _b carbon atoms, for example, methylsulfonyl group, ethylsulfonyl group, n- Specific examples include a propylsulfonyl group, an i-propylsulfonyl group, an n-butylsulfonyl group, an i-butylsulfonyl group, an s-butylsulfonyl group, a tert-butylsulfonyl group, and the range of each designated number of carbon atoms. Selected.

The notation of C _a -C _b haloalkylsulfonyl in the present specification represents a haloalkyl-SO ₂ -group having the above-mentioned meaning consisting of _a to _b carbon atoms, such as a difluoromethylsulfonyl group or a trifluoromethylsulfonyl group. Chlorodifluoromethylsulfonyl group, bromodifluoromethylsulfonyl group, 2,2,2-trifluoroethylsulfonyl group, 1,1,2,2-tetrafluoroethylsulfonyl group, 2-chloro-1,1,2-trimethyl Specific examples include a fluoroethylsulfonyl group and the like, and each is selected within the range of the designated number of carbon atoms.

The notation of C _a -C _b alkylamino in the present specification represents an amino group in which one of the hydrogen atoms is substituted with an alkyl group having the above-mentioned meaning consisting of _a to _b carbon atoms, for example, a methylamino group , Ethylamino group, n-propylamino group, i-propylamino group, n-butylamino group, i-butylamino group, tert-butylamino group and the like. Selected by range.

In the present specification, the notation of di (C _a -C _b alkyl) amino has the above-mentioned meaning that the number of carbon atoms which may be the same or different from each other is ab. Represents an amino group substituted by an alkyl group, such as dimethylamino group, ethyl (methyl) amino group, diethylamino group, n-propyl (methyl) amino group, i-propyl (methyl) amino group, di (n-propyl) Specific examples include an amino group, a di (n-butyl) amino group, and the like, and each is selected within the range of the designated number of carbon atoms.

The notation of C _a -C _b alkylimino in the present specification represents an alkyl-N = group having the above-mentioned meaning consisting of _a to _b carbon atoms, for example, methylimino group, ethylimino group, n-propylimino group. Specific examples include i-propylimino group, n-butylimino group, i-butylimino group, s-butylimino group, and the like, and each is selected within the range of the number of carbon atoms designated.

The notation of C _a -C _b alkoxyimino in the present specification represents an alkoxy-N = group having the above-mentioned meaning consisting of _a to _b carbon atoms, for example, methoxyimino group, ethoxyimino group, n-propyl. Specific examples include an oxyimino group, an i-propyloxyimino group, an n-butyloxyimino group, and the like, and each is selected within the range of the designated number of carbon atoms.

The notation of C _a -C _b alkylcarbonyl in the present specification represents an alkyl-C (O) -group having the above-mentioned meaning consisting of _a to _b carbon atoms, for example, acetyl group, propionyl group, butyryl group. , Isobutyryl group, valeryl group, isovaleryl group, 2-methylbutanoyl group, pivaloyl group, hexanoyl group, heptanoyl group, and the like, and specific examples thereof are selected within the range of the number of carbon atoms designated.

The notation of C _a -C _b haloalkylcarbonyl in the present specification represents a haloalkyl-C (O) -group having the above-mentioned meaning consisting of _a to _b carbon atoms, such as a fluoroacetyl group, a chloroacetyl group, Difluoroacetyl group, dichloroacetyl group, trifluoroacetyl group, chlorodifluoroacetyl group, bromodifluoroacetyl group, trichloroacetyl group, pentafluoropropionyl group, heptafluorobutanoyl group, 3-chloro-2,2-dimethylpropanoyl group Etc. are given as specific examples, and each is selected within the range of the designated number of carbon atoms.

The notation of C _a -C _b cycloalkylcarbonyl in the present specification represents a cycloalkyl-C (O) -group having the above-mentioned meaning consisting of _a to _b carbon atoms, such as cyclopropylcarbonyl group, 2 Specific examples include -methylcyclopropylcarbonyl group, cyclobutylcarbonyl group, etc., and each is selected within the range of the designated number of carbon atoms.

In the present specification, the expression C _a -C _b halocycloalkylcarbonyl represents a halocycloalkyl-C (O) — group having the above-mentioned meaning consisting of _a to _b carbon atoms. Specific examples include a dichlorocyclopropylcarbonyl group, a 2,2-dichloro-1-methylcyclopropylcarbonyl group, and the like, which are selected in the range of the designated number of carbon atoms.

The notation of C _a -C _b alkoxycarbonyl in the present specification represents an alkyl-O—C (O) — group having the above-mentioned meaning consisting of _a to _b carbon atoms, for example, methoxycarbonyl group, ethoxycarbonyl Group, n-propyloxycarbonyl group, i-propyloxycarbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl group, tert-butoxycarbonyl group and the like, and specific ranges of the number of carbon atoms are designated. Selected.

The notation of C _a -C _b haloalkoxycarbonyl in the present specification represents a haloalkyl-O—C (O) — group having the above-mentioned meaning consisting of _a to _b carbon atoms, such as a chloromethoxycarbonyl group, Specific examples include 2-chloroethoxycarbonyl group, 2,2-difluoroethoxycarbonyl group, 2,2,2-trifluoroethoxycarbonyl group, 2,2,2-trichloroethoxycarbonyl group, and the like. Selected in the range of the number of carbon atoms.

The notation of C _a -C _b alkylaminocarbonyl in the present specification represents a carbamoyl group in which one of the hydrogen atoms is substituted with an alkyl group having the above-mentioned meaning consisting of _a to _b carbon atoms, for example, methylcarbamoyl Group, ethylcarbamoyl group, n-propylcarbamoyl group, i-propylcarbamoyl group, n-butylcarbamoyl group, i-butylcarbamoyl group, s-butylcarbamoyl group, tert-butylcarbamoyl group, etc. Is selected within the range of the specified number of carbon atoms.

In the present specification, the expression C _a -C _b haloalkylaminocarbonyl represents a carbamoyl group in which one of the hydrogen atoms is substituted with a haloalkyl group having the above-described meaning consisting of _a to _b carbon atoms, for example, 2-fluoro Specific examples include ethylcarbamoyl group, 2-chloroethylcarbamoyl group, 2,2-difluoroethylcarbamoyl group, 2,2,2-trifluoroethylcarbamoyl group, etc. Is done.

In the present specification, the notation of di (C _a -C _b alkyl) aminocarbonyl means in the above meaning that the number of carbon atoms which may be the same or different from each other is _a to _b. Represents a carbamoyl group substituted by an alkyl group, such as N, N-dimethylcarbamoyl group, N-ethyl-N-methylcarbamoyl group, N, N-diethylcarbamoyl group, N, N-di (n-propyl) carbamoyl Specific examples include a group, an N, N-di (n-butyl) carbamoyl group, and the like, and each is selected within the range of the designated number of carbon atoms.

In the present specification, C _a -C _b alkylaminosulfonyl represents a sulfamoyl group in which one of the hydrogen atoms is substituted with an alkyl group having the above-mentioned meaning consisting of _a to _b carbon atoms. Famoyl group, ethylsulfamoyl group, n-propylsulfamoyl group, i-propylsulfamoyl group, n-butylsulfamoyl group, i-butylsulfamoyl group, s-butylsulfamoyl group, Specific examples include a tert-butylsulfamoyl group and the like, and each is selected within the range of the designated number of carbon atoms.

In the present specification, the notation of di (C _a -C _b alkyl) aminosulfonyl means in the above meaning that the number of carbon atoms which may be the same or different from each other is _a to _b. Represents a sulfamoyl group substituted by an alkyl group, such as N, N-dimethylsulfamoyl group, N-ethyl-N-methylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-di- Specific examples include (n-propyl) sulfamoyl group, N, N-di (n-butyl) sulfamoyl group and the like, and each is selected within the range of the designated number of carbon atoms.

Herein optionally substituted with ^{R 5a} _(C ^{a ~C} _b) ^alkyl, optionally substituted with ^{R 10a} _(C ^{a ~C} _b) ^alkyl, optionally substituted with ^{R 15a} _(C ^a ~ C _b) ^alkyl, optionally substituted with ^{R 15b} _(C a ^~C _b) ^alkyl, optionally substituted with ^{R 15c} _(C a ^~C _b) ^alkyl, optionally substituted with ^{R 15d} _{(C a} -C _b) ^alkyl, optionally substituted with ^{R 20} _(C a ~C _b) ^alkyl, optionally substituted with ^{R 28} _(C a ~C _b) alkyl or optionally substituted with ^{R 28a} (C _{a to} C _b ) Alkyl and the like are represented by any R ^5a , R ^10a , R ^15a , R ^15b , R ^15c , R ^15d , R ²⁰ , R ²⁸ or R ^28a , and a hydrogen atom bonded to a carbon atom is arbitrary. Number of carbon atoms replaced by Represents an alkyl group having the above-mentioned meaning consisting of a to b, and is selected within the range of each designated number of carbon atoms. At this time, there are two or more substituents R ^5a , R ^10a , R ^15a , R ^15b , R ^15c , R ^15d , R ²⁰ , R ²⁸ or R ^28a on each (C _a -C _b ) alkyl group. when each ^{R 5a, R 10a, R 15a} , R 15b, R 15c, R 15d, R 20, R 28 or ^{R 28a} may be the same or different from each other.

Herein optionally substituted with ^{R 10a} _(C ^{a ~C} _b) ^cycloalkyl, optionally substituted with ^{R 15a} _(C ^{a ~C} _b) ^cycloalkyl, optionally substituted with ^{R 15b} (C _a -C _b) ^cycloalkyl, substituted optionally substituted with ^{R 15c} _(C a ~C _b) ^cycloalkyl, optionally substituted with ^{R 15d} _(C a ~C _b) ^cycloalkyl, optionally in ^{R 20} been _(C a _{~C b)} optionally substituted cycloalkyl, or ^{R 28} _(C a _{~C b)} notation cycloalkyl or the like, any of ^{R 10a, R 15a, R 15b} , R 15c, R 15d , the R ²⁰ or R ^28, the number of carbon atoms bonded to hydrogen atoms are optionally replaced by a carbon atom a cycloalkyl group is the meaning of consisting a~b pieces, each of the specified number of carbon atoms It is selected in the enclosed. At this time, when two or more substituents R ^10a , R ^15a , R ^15b , R ^15c , R ^15d , R ²⁰ or R ²⁸ on each (C _a -C _b ) cycloalkyl group are present, each R ^10a , R ^15a , R ^15b , R ^15c , R ^15d , R ²⁰ or may be the same as or different from each other, and the substitution position may be a ring structure part, a side chain part, or both May be.

Herein optionally substituted with ^{R 5a} _(C ^{a ~C} _b) ^alkenyl, optionally substituted with ^{R 15a} _(C ^{a ~C} _b) ^alkenyl, optionally substituted with ^{R 15b} _(C a ~ C _b) ^alkenyl, optionally substituted with ^{R 15c} _(C a ^~C _b) ^alkenyl, optionally substituted with ^{R 15d} _(C a ^~C _b) ^alkenyl, optionally substituted with ^{R 20} _{(C a} -C _b) ^alkenyl, optionally substituted with ^{R 28} _(C a ~C _b) alkenyl or optionally substituted with ^{R 28a} _(C ^a ~C _b) notation alkenyl or the like, any of ^R 5a, R ^15a , R ^15b , R ^15c , R ^15d , R ²⁰ , R ^28, or R ^28a is an alkenyl having the above-mentioned meaning, wherein the hydrogen atom bonded to the carbon atom is arbitrarily substituted, comprising ab Group And it is selected from the range of the specified number of carbon atoms. At this time, when two or more substituents R ^5a , R ^15a , R ^15b , R ^15c , R ^15d , R ²⁰ , R ²⁸ or R ^28a on each (C _a -C _b ) alkenyl group are present, R ^5a , R ^15a , R ^15b , R ^15c , R ^15d , R ²⁰ , R ²⁸ or R ^28a may be the same as or different from each other.

Optionally substituted with R ^15a _(C ^a ~C _b) ^{cycloalkenyl,} optionally substituted with ^{R 15b} _(C a ^~C _b) ^{cycloalkenyl,} optionally substituted with ^{R 15c} _(C a ^~C _b ) ^{cycloalkenyl,} optionally substituted with ^{R 15d} _(C a ^~C _b) ^{cycloalkenyl,} optionally substituted with ^{R 20} _(C a ^~C _b) ^{cycloalkenyl,} optionally substituted with ^{R 28} (C _{a to} C _b ) cycloalkenyl or (C _{a to} C _b ) cycloalkenyl optionally substituted with R ^28a is any R ^15a , R ^15b , R ^15c , R ^15d , R ²⁰ , R ²⁸ or by R ^28a, represents a cycloalkenyl group having a carbon atom bonded to a hydrogen atom is optionally substituted carbon atom which is the meaning of consisting a~b pieces, each of the specified number of carbon atoms It is selected in the enclosed. At this time, when two or more substituents R ^15a , R ^15b , R ^15c , R ^15d , R ²⁰ , R ²⁸ or R ^28a on each (C _a -C _b ) cycloalkenyl group are present, each R ^15a , R ^15b , R ^15c , R ^15d , R ²⁰ , R ²⁸ or R ^28a may be the same as or different from each other, and the substitution position may be a ring structure part, a side chain part, or May be in both.

Herein optionally substituted with ^{R 5a} _(C ^{a ~C} _b) ^alkynyl, optionally substituted with ^{R 15a} _(C ^{a ~C} _b) ^alkynyl, optionally substituted with ^{R 15b} _(C a ~ C _b) ^alkynyl, optionally substituted with ^{R 15c} _(C a ^~C _b) ^alkynyl, optionally substituted with ^{R 15d} _(C a ^~C _b) ^alkynyl, optionally substituted with ^{R 20} _{(C a} -C _b) ^alkynyl, optionally substituted with ^{R 28} _(C a ~C _b) alkynyl or optionally substituted with ^{R 28a} _(C ^a ~C _b) notation alkynyl or the like, any of ^R 5a, R ^{15a, R 15b, R 15c,} R 15d, by R ^{20, R 28} or ^{R 28a,} the meaning of the number of carbon atoms in which the hydrogen atoms bonded to carbon atom is optionally substituted is more a~b number alkynyl Group And it is selected from the range of the specified number of carbon atoms. At this time, when two or more substituents R ^5a , R ^15a , R ^15b , R ^15c , R ^15d , R ²⁰ , R ²⁸ or R ^28a on each (C _a -C _b ) alkynyl group are present, R ^5a , R ^15a , R ^15b , R ^15c , R ^15d , R ²⁰ , R ²⁸ or R ^28a may be the same as or different from each other.

^{[R 13b} herein by forming the alkenylene chain alkylene chain or _C 2 -C ₇ of _C 2 -C ₇ together with ^{R 14b,} 3 together with the nitrogen atom ^{to which R 13b} and ^{R 14b} are bonded An 8-membered ring may be formed, in which case the alkylene chain or alkenylene chain may contain one oxygen atom, sulfur atom or nitrogen atom.]
^{[R 18b} is by forming alkenylene chain alkylene chain or _C 2 -C ₇ of _C 2 -C ₇ together with ^{R 19b,} 3 to 8-membered ring together with the nitrogen atom ^{to which R 13b} and ^{R 14b} are bonded Wherein the alkylene chain or alkenylene chain may contain one oxygen atom, sulfur atom or nitrogen atom,
^{[R 18 d} is by forming alkenylene chain alkylene chain or _C 2 -C ₇ of _C 2 -C ₇ together with ^{R 19d,} 3 to 8-membered ring together with the nitrogen atom ^{to which R 13b} and ^{R 14b} are bonded Wherein the alkylene chain or alkenylene chain may contain one oxygen atom, sulfur atom or nitrogen atom,
Specific examples of the notation such as aziridine, azetidine, azetidin-2-one, pyrrolidine, pyrrolidin-2-one, oxazolidine, oxazolidine-2-one, oxazolidine-2-thione, thiazolidine, thiazolidine-2-one, thiazolidine -2-thione, imidazolidine, imidazolidine-2-one, imidazolidine-2-thione, piperidine, piperidin-2-one, piperidine-2-thione, 2H-3,4,5,6-tetrahydro-1, 3-Oxazin-2-one, 2H-3,4,5,6-tetrahydro-1,3-oxazine-2-thione, morpholine, 2H-3,4,5,6-tetrahydro-1,3-thiazine- 2-one, 2H-3,4,5,6-tetrahydro-1,3-thiazine-2-thione, thiomorpholine, pe Tetrahydropyrimidine-2-one, piperazine, homopiperidine, homopiperidine-2-one, heptamethyleneimine, and the like, may be selected from the range of the number of each of the specified atoms.

^{[R 14e} herein by forming the alkenylene chain alkylene chain or _C 2 -C ₇ of _C 2 -C ₇ together with ^{R 14f,} 3 together with the carbon atom ^{to which R 14e} and ^{R 14f} are bonded An 8-membered ring may be formed, in which case the alkylene chain or alkenylene chain may contain 1, 2 or 3 oxygen atoms, sulfur atoms or nitrogen atoms.]
Specific examples of the notation include, for example, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, oxetane-3-ylidene, thietan-3-ylidene, dihydrofuran-3-ylidene, dihydrothiophen-3-ylidene, Dihydropyran-3-ylidene, dihydropyran-4-ylidene, dihydrothiopyran-3-ylidene, dihydrothiopyran-4-ylidene, thiazolidine-2-ylidene, 2,3-dihydrothiazol-2-ylidene, imidazolidine- 2-ylidene, 2,3-dihydroimidazol-2-ylidene, 2,3-dihydro-1,3,4-thiadiazol-2-ylidene, 1,2-dihydropyridin-2-ylidene, 2,3-dihydropyridazine 3-Ilidene, 1,2-dihydropyrazin-2-y Den, 1,2-dihydro-2-ylidene, 6H-2,3-dihydro-1,3,4-thiadiazine-2-ylidene and the like, may be selected from the range of the number of each of the specified atoms.

  The compound of the present invention can be produced by the following method.

  Manufacturing method A

Formula (6) [wherein A ¹ , R ² , R ³ , R ⁴ , R ^6b , R ^a and n represent the same meaning as described above. And a compound represented by the formula (7) [wherein A ¹ , R ² , R ³ , R ⁴ , R ^a and n represent the same meaning as described above]. The compound represented by this can be obtained.

  As the acid, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, trifluoroacetic acid and the like can be used. As the base, potassium carbonate, sodium hydroxide or the like can be used.

  This reaction may be carried out without solvent, but a solvent may be used. For example, polar solvents such as acetonitrile and water, alcohols such as methanol, ethanol, propanol, 2-propanol and ethylene glycol, ethers such as diethyl ether, tetrahydrofuran and diphenyl ether, and aromatic hydrocarbons such as benzene, toluene and xylene , Halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride, and aliphatic hydrocarbons such as pentane and n-hexane. These solvents may be used alone or as a mixture of two or more thereof.

  The reaction temperature can be set to any temperature from −60 ° C. to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually arbitrary in the range of 5 minutes to 100 hours. Can be set.

The compound represented by the formula (7) thus obtained is converted into the formula (8-1) [wherein R ^7b represents the same meaning as described above. And a compound represented by formula (9) [wherein A ¹ , R ² , R ³ , R ⁴ , R ^7b , R ^a and n represent the same meaning as described above]. This invention compound represented by this can be synthesize | combined. In this reaction, the compound represented by the formula (8-1) can be used in the range of 0.5 to 50 equivalents with respect to 1 equivalent of the compound represented by the formula (7). If necessary, a base such as potassium carbonate, triethylamine, pyridine, 4- (dimethylamino) pyridine can be used. This reaction may be carried out without solvent, but a solvent may be used, for example, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, 1,3-dimethyl-2- Polar solvents such as imidazolinone, alcohols such as methanol, ethanol, propanol, 2-propanol and ethylene glycol, ethers such as diethyl ether, tetrahydrofuran and diphenyl ether, aromatic hydrocarbons such as benzene, toluene and xylene, methylene chloride , Halogenated hydrocarbons such as chloroform and carbon tetrachloride, and aliphatic hydrocarbons such as pentane and n-hexane. These solvents may be used alone or as a mixture of two or more thereof.

  The reaction temperature can be set to any temperature from −60 ° C. to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually arbitrary in the range of 5 minutes to 100 hours. Can be set.

  Some of the compounds represented by formula (8-1) are known compounds, and some of them are commercially available. Others can be easily synthesized according to known methods described in the literature.

Moreover, the compound represented by Formula (7) is replaced with Formula (8-2) [wherein R ^7b represents the same meaning as described above. The compound of the present invention represented by formula (9) can also be synthesized by reacting the compound represented by formula (9) with a condensing agent. In this reaction, 1 to 4 equivalents of WSC {1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride}, CDI (carbonyldiimidazole) per 1 equivalent of the compound represented by formula (8-2) ) And the like can be used. Moreover, the compound represented by Formula (8-2) can be used in 0.5-50 equivalent with respect to 1 equivalent of compounds represented by Formula (7). If necessary, a base such as potassium carbonate, triethylamine, pyridine, 4- (dimethylamino) pyridine can be used.

  This reaction may be carried out without solvent, but a solvent may be used, for example, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, 1,3-dimethyl-2- Polar solvents such as imidazolinone, alcohols such as methanol, ethanol, propanol, 2-propanol and ethylene glycol, ethers such as diethyl ether, tetrahydrofuran and diphenyl ether, aromatic hydrocarbons such as benzene, toluene and xylene, methylene chloride , Halogenated hydrocarbons such as chloroform and carbon tetrachloride, and aliphatic hydrocarbons such as pentane and n-hexane. These solvents may be used alone or as a mixture of two or more thereof.

  The reaction temperature can be set to any temperature from −60 ° C. to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually arbitrary in the range of 5 minutes to 100 hours. Can be set.

  Some of the compounds represented by formula (8-2) are known compounds, and some of them are commercially available. Others can be synthesized according to known methods described in the literature.

  Manufacturing method B

Formula (2-12) [wherein R ³ , R ⁴ , R ^7b and R ^a represent the same meaning as described above. And a compound represented by formula (2-2) [wherein A ¹ , R ² and n represent the same meaning as described above, and L ₁ represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, —B (OH ) ₂ groups or -B (OR ⁵¹ ) ₂ groups (wherein R ⁵¹ represents a hydrogen atom or C _{1 to} C ₆ alkyl which may be the same or different, or two R ⁵¹ together represent- CH ₂ CH ₂ — or —C (CH ₃ ) ₂ C (CH ₃ ) ₂ — may be formed). The compound of the present invention represented by the formula (9) can be obtained by reacting the compound represented by formula (9) in the presence of a catalyst and a base.

  The amount of the compound represented by the formula (2-2) can be used in the range of 0.8 to 5 equivalents relative to 1 equivalent of the compound represented by the formula (2-12).

  Some of the compounds represented by the formula (2-2) used here are known compounds, and some of them are available as commercial products. Others can be easily synthesized according to the methods described in the literature.

  Examples of the catalyst that can be used in this reaction include palladium catalysts such as palladium-carbon, palladium chloride, palladium acetate, bis (triphenylphosphine) palladium dichloride, tetrakis (triphenylphosphine) palladium, or copper metal, copper acetate (I). And copper catalysts such as copper (II) acetate, copper (I) oxide, copper (II) oxide and copper iodide. The amount of the catalyst used is 0.001 to 1.0 equivalent, preferably 0.01 to 0.5 equivalent, more preferably 0.05 to 1 equivalent to 1 equivalent of the compound represented by formula (2-12). It can be used in the range of 0.2 equivalents.

  Examples of the base used include tertiary amine compounds such as pyridine, diisopropylethylamine, and triethylamine, and inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, and sodium bicarbonate. . The usage-amount of a base can be used in the range of 0.1-10.0 equivalent with respect to 1 equivalent of compounds represented by Formula (2-12).

  This reaction can be carried out without solvent, but a solvent may be used. For example, polar solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolinone, water, methanol, ethanol, propanol, 2-propanol, ethylene glycol Alcohols such as diethyl ether, tetrahydrofuran and diphenyl ether, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride, pentane and n-hexane And aliphatic hydrocarbons. These solvents may be used alone or as a mixture of two or more thereof.

  The reaction temperature can be set to any temperature from −60 ° C. to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually arbitrary in the range of 5 minutes to 100 hours. Can be set.

  Manufacturing method C

A compound represented by the formula (9), diphosphorus pentasulfide, diphosphorus pentasulfide-HMDO (hexamethyldisiloxane), Lawesson's Reagent; 2,4-bis (4-methoxyphenyl) -1 , 3,2,4-dithiadiphosphetane-2,4-disulfide) and the like to react with the compound represented by formula (35) [wherein A ¹ , R ² , R ³ , R ⁴ , R ^7b , R ^a and n represent the same meaning as described above. This invention compound represented by this can be obtained.

  The sulfurizing agent used in this reaction can be used in the range of 0.5 to 50 equivalents relative to 1 equivalent of the compound represented by formula (9).

  If necessary, a base such as potassium carbonate, triethylamine, pyridine, 4- (dimethylamino) pyridine can be used.

  This reaction can be carried out without solvent, but a solvent may be used. For example, polar solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolinone, water, methanol, ethanol, propanol, 2-propanol, ethylene glycol Alcohols such as diethyl ether, tetrahydrofuran and diphenyl ether, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride, pentane and n-hexane And aliphatic hydrocarbons. These solvents may be used alone or as a mixture of two or more thereof.

  The reaction temperature can be set to any temperature from −60 ° C. to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually arbitrary in the range of 5 minutes to 100 hours. Can be set.

  Manufacturing method D

Formula (13) [wherein A ¹ , R ² , R ³ , R ⁴ and n represent the same meaning as described above. The compound represented by formula (8-1) or the compound represented by formula (8-2) is reacted with the compound represented by formula (8-1) using the same method as in Production Method A. 41) [wherein A ¹ , R ² , R ³ , R ⁴ , R ^7b and n represent the same meaning as described above. This invention compound represented by this can be obtained.

Subsequently, the compound represented by the formula (41) is represented by the formula (5) [wherein R ^a represents the same meaning as described above, and J ^b represents a halogen atom, —OH, —OSO ₂ CH ₃ , —OSO ₂ CF _3. Represents a leaving group. The compound of the present invention represented by the formula (9) can also be obtained by reacting with the compound represented by formula (9).

  In this reaction, the compound represented by the formula (5) can be used in the range of 0.5 to 50 equivalents with respect to 1 equivalent of the compound represented by the formula (41). If necessary, bases such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, etc., potassium carbonate, triethylamine, pyridine, 4- (dimethylamino) pyridine, sodium hydride, sodium hydroxide, potassium hydroxide, or diethyl Mitsunobu reaction using azodicarboxylate and triphenylphosphine can be used.

  This reaction can be carried out without solvent, but a solvent may be used. For example, polar solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolinone, water, methanol, ethanol, propanol, 2-propanol, ethylene glycol Alcohols such as diethyl ether, tetrahydrofuran and diphenyl ether, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride, pentane and n-hexane And aliphatic hydrocarbons. These solvents may be used alone or as a mixture of two or more thereof.

  The reaction temperature can be set to any temperature from −60 ° C. to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually arbitrary in the range of 5 minutes to 100 hours. Can be set.

  Some of the compounds represented by formula (5) are known compounds, and some of them are commercially available. Others can be synthesized according to known methods described in the literature.

  Manufacturing method E

Formula (9-2) [wherein A ¹ , R ² , R ³ , R ⁴ , R ^a , R ^11b , R ^12b and n represent the same meaning as described above. In accordance with the method described in Experimental Chemistry Course (5th edition) 2005 (Japan Chemical Society, Maruzen Co., Ltd.), page 415, etc., the compound represented by the formula (9- 3) [wherein A ¹ , R ² , R ³ , R ⁴ , R ^a , R ^11b , R ^12b and n represent the same meaning as described above. This invention compound represented by this can be obtained. Similarly, the compound of the present invention represented by the formula (9-2) can also be obtained from the compound represented by the formula (9-3).

  Manufacturing method F

Formula (9-4) [wherein A ¹ , R ² , R ³ , R ⁴ , R ^12b , R ^a and n represent the same meaning as described above. The compound represented by formula (9-5) [wherein A ¹ , R ² , R ³ , R ⁴ , R ^12b is a geometric isomer of the oxime moiety using the same method as in Production Method I. , R ^a and n represent the same meaning as described above. This invention compound represented by this can be obtained. Similarly, the compound of the present invention represented by the formula (9-4) can also be obtained from the compound represented by the formula (9-5).

  The reaction from production method A to production method F may be carried out in an inert gas atmosphere such as nitrogen or argon if necessary.

  In the reaction from production method A to production method F, the reaction mixture after completion of the reaction is directly concentrated, or dissolved in an organic solvent, concentrated after washing with water, or poured into ice water and concentrated after extraction with an organic solvent, followed by normal post-treatment. The objective compound of the present invention can be obtained. Moreover, when the necessity for purification arises, it can be separated and purified by any purification method such as recrystallization, column chromatograph, thin layer chromatograph, liquid chromatographic fractionation and the like.

  The compound represented by the formula (6) used in the production method A can be synthesized, for example, as shown in the following reaction formula 1 to reaction formula 2.

  Reaction formula 1

Formula (2-1) [wherein R ³ and R ⁴ represent the same meaning as described above, and R ⁵⁰ represents a C _{1 to} C ₆ alkyl group. ] Can be synthesized by a known method such as Sinlet 2004, Vol. 4, 703.

That is, the compound represented by the formula (2-1) is converted into a known formula (2-) according to a known method known in the literature, for example, the method described in Journal of Organic Chemistry 2004, 69, 5578. 2) [wherein A ¹ , R ² and n represent the same meaning as described above, and L ₁ represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, —B (OH) ₂ group or —B (OR ⁵¹ ) _2. A group (wherein R ⁵¹ represents a hydrogen atom or C _{1 to} C ₆ alkyl which may be the same or different, or two R ⁵¹ together represent —CH ₂ CH ₂ — or —C (CH ₃ ) ₂ C (CH ₃ ) ₂ — may be formed). ] In the presence of a metal catalyst such as copper and a base, or in the presence of a transition metal catalyst such as palladium and a base, the compound represented by formula (2-3) [in the formula, A ¹ , R ² , R ³ , R ⁴ and n represent the same meaning as described above, and R ⁵⁰ represents a C _{1 to} C ₆ alkyl group. Can be obtained.

In addition, the compound represented by the formula (2-3) has the formula (2-4) [wherein R ³ , R ⁴ and R ⁵⁰ have the same meaning as described above, and R ⁵¹ represents a methoxy group, an ethoxy group, dimethyl group, Represents a leaving group such as an amino group. And a compound represented by formula (2-5) [wherein A ¹ , R ² and n represent the same meaning as described above. Can be synthesized according to a method known in the literature, for example, the method described in Journal of Heterocyclic Chemistry 1987, Vol. 24, page 1669. The compound represented by the formula (2-4) is obtained by a known method such as Journal of Heterocyclic Chemistry 1987, Vol. 24, page 693, and the compound represented by the formula (2-5) is represented by Journal of Medicinal. Chemistry 2002, 45, 5397, etc. can be synthesized.

Further, the compound represented by the formula (2-3) is subjected to a hydrolysis reaction according to a known method known in the literature to obtain a compound represented by the formula (2) [wherein A ¹ , R ² , R ³ , R ⁴ and n Represents the same meaning as described above. The compound represented by this can be manufactured.

  Reaction formula 2

The compound represented by formula (2) is diphenylphosphoryl azide (DPPA) and formula (3) [wherein R ^6b represents the same meaning as described above. In the formula (4), A ¹ , R ² , R ³ , R ⁴ , R ^6b and n have the same meaning as described above. The compound represented by this can be obtained.

  In this reaction, DPPA can be used in the range of 0.5 to 50 equivalents relative to 1 equivalent of the compound represented by formula (2), and the compound represented by formula (3) is represented by formula (2). Can be used in the range of 1 equivalent to the amount of solvent relative to 1 equivalent of the compound represented by formula (1). If necessary, a base such as potassium carbonate, triethylamine, pyridine, 4- (dimethylamino) pyridine can be used.

  This reaction can be carried out without solvent, but a solvent may be used. For example, polar solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolinone, water, methanol, ethanol, propanol, 2-propanol, ethylene glycol Alcohols such as diethyl ether, tetrahydrofuran and diphenyl ether, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride, pentane and n-hexane And aliphatic hydrocarbons. These solvents may be used alone or as a mixture of two or more thereof.

  The reaction temperature can be set to any temperature from −60 ° C. to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually arbitrary in the range of 5 minutes to 100 hours. Can be set.

  Some of the compounds represented by formula (3) are known compounds, and some of them are commercially available. Others can be synthesized according to known methods described in the literature.

Continued formula (4), compounds represented by using the same method as a production method D, the formula (5) [wherein R ^a are as defined above, J ^b is a halogen atom, -OH, - It represents a leaving group such as OSO ₂ CH ₃ or —OSO ₂ CF ₃ . In the formula (6), A ¹ , R ² , R ³ , R ⁴ , R ^6b , R ^a and n have the same meaning as described above. The compound represented by this can be obtained.

  The compound represented by Formula (2-12) used in Production Method B can be synthesized, for example, as follows.

  Reaction formula 3

Formula (2-6) [wherein R ³ , R ⁴ and R ⁵⁰ represent the same meaning as described above, and P ¹ represents tertiary butyl, benzyl, 4-methoxybenzyl, acetyl, benzoyl, benzenesulfonyl, p-toluenesulfonyl. Represents a protecting group such as methanesulfonyl, methoxymethyl or methylthiomethyl. ] Can be synthesized by known methods such as Journal of Heterocyclic Chemistry 1987, 24, 693.

By hydrolyzing the compound represented by the formula (2-6) according to a known method known in the literature, the formula (2-7) [wherein R ³ , R ⁴ and P ¹ are the same as described above. Represents meaning. The compound represented by this can be manufactured.

Subsequently, the compound represented by the formula (2-7) is used in the same manner as in the above reaction formula 2, and the formula (2-8) [wherein R ³ , R ⁴ , R ^6b and P ¹ are the same as above. Represents meaning. ] Can be synthesized.

Next, the compound represented by the formula (2-8) and the compound represented by the formula (5) are reacted in the same manner as in the reaction formula 2, thereby obtaining the formula (2-9) [in the formula R ³ , R ⁴ , R ^a , R ^6b and P ¹ represent the same meaning as described above. ] Can be synthesized.

Furthermore, from the compound represented by formula (2-9), formula (2-10) [wherein R ³ , R ⁴ , R ^a and P ¹ represent the same meaning as described above in accordance with production method A. The compound represented by formula (2-11) [wherein R ³ , R ⁴ , R ^7b , R ^a and P ¹ represent the same meaning as described above. ] Can be synthesized.

By deprotecting the compound represented by the formula (2-11) thus synthesized with an acid, the formula (2-12) [wherein R ³ , R ⁴ , R ^7b and R ^a are as defined above. Represents the same meaning. ] Can be synthesized.

  The compound represented by the formula (7) used in the production method A can be synthesized, for example, as follows.

  Reaction formula 4

Formula (2-13) [wherein R ³ , R ⁴ and R ^a represent the same meaning as described above. ] Can be synthesized by a known method such as International Publication No. 2011/048082.

  The compound represented by the formula (7) is synthesized by reacting the compound represented by the formula (2-13) and the compound represented by the formula (2-2) in the same manner as in the production method B. be able to.

  The compound represented by Formula (13) used in Production Method D can be synthesized, for example, as follows.

  Reaction formula 5

By reacting the compound represented by the formula (2) with a nitrating agent in the presence of an acid anhydride, the formula (2-14) [wherein A ¹ , R ² , R ³ , R ⁴ and n are the same as above] Represents meaning. ] Can be synthesized.

  In addition, the compound represented by the formula (2-14) is obtained by converting the compound represented by the formula (2-15) into a method known in the literature, for example, Journal of Heterocyclic Chemistry 1981, Vol. 18, p. According to the method described, it can be synthesized by reacting. The compound represented by the formula (2-15) can be synthesized by a known method such as European Journal of Organic Chemistry 2004, No. 4, page 695.

  Furthermore, the compound represented by Formula (2-14) reacts the compound represented by Formula (2-16) with the compound represented by Formula (2-2) in the same manner as in Production Method B. Can be synthesized.

  Some of the compounds represented by the formula (2-16) are known compounds, and some of them are available as commercial products. Others can be synthesized according to known methods described in the literature.

Subsequently, the compound represented by the formula (2-14) is converted into the formula (13) by a known nitro group reduction method, wherein A ¹ , R ² , R ³ , R ⁴ and n have the same meaning as described above. Represent. ] Can be synthesized.

  The compound represented by the formula (13) is obtained by converting the compound represented by the formula (2) into a diphenyl phosphate according to a method known in the literature, for example, the method described in Pharmaceutical Journal 1990, 110, 457, etc. Formula (2-14b), which can be synthesized by reacting with azide (DPPA), is further reacted according to a method known in the literature, for example, tetrahedron 2013, 69, 395, etc. Can be synthesized.

  Reaction formula 6

By reacting the compound represented by the formula (2-7) according to a method known in the literature, for example, the method described in Tetrahedron Letters 2003, 44, 7629, etc., the formula (2-17) [Wherein R ³ , R ⁴ and P ¹ represent the same meaning as described above. ] Can be synthesized.

Subsequently, the compound represented by the formula (2-17) is converted into a method known in the literature, for example, according to the method described in Experimental Science Course 5th Edition (Edited by Chemical Society of Japan) 2005, 14, 374 pages, etc. Formula (2-18) [In formula, M represents alkali metals, such as sodium and potassium. Or a compound represented by formula (2-19): wherein M represents the same meaning as described above. And a compound represented by formula (2-20) [wherein R ³ , R ⁴ and P ¹ represent the same meaning as described above. ] Can be synthesized.

Furthermore, by reacting the compound represented by the formula (2-20) using the same method as the production method A, the compound represented by the formula (2-21) [wherein R ³ , R ⁴ , R ^7b and P ¹ are Represents the same meaning as above. ] Can be synthesized.

By deprotecting the compound represented by the formula (2-21) synthesized in this way with an acid or a base, the formula (2-22) [wherein R ³ , R ⁴ and R ^7b are the same as described above. Represents meaning. ] Can be synthesized.

  Reaction formula 7

Formula (8-3) [wherein R ^11b , R ⁵⁰ and J ^b represent the same meaning as described above, and R ⁶⁰ and R ⁶¹ each independently represent a hydrogen atom, a C _{1 to} C ₆ alkyl group or R ^15c. Represents a (C ₁ -C ₆ ) alkyl group optionally substituted with, and t represents an integer of 0-6. ] Can be synthesized according to a known method such as German Patent Application Publication No. 3220524.

Formula (8-4) [wherein R ^16c represents the same meaning as described above. Some of the compounds represented by] are known compounds, and some of them are commercially available. Others can be synthesized according to known methods described in the literature.

By reacting the compound represented by the formula (8-3) with the compound represented by the formula (8-4), the compound represented by the formula (8-5) [wherein R ^11b , R ^16c , R ⁵⁰ , R ⁶⁰ , R ⁶¹ and t have the same meaning as described above. The compound represented by this can be obtained.

  In this reaction, the compound represented by the formula (8-4) can be used in the range of 0.5 to 50 equivalents relative to 1 equivalent of the compound represented by the formula (8-3). If necessary, bases such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, etc., potassium carbonate, triethylamine, pyridine, 4- (dimethylamino) pyridine, sodium hydride, sodium hydroxide, potassium hydroxide, or diethyl Mitsunobu reaction using azodicarboxylate and triphenylphosphine can be used.

  This reaction can be carried out without solvent, but a solvent may be used. For example, polar solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolinone, water, methanol, ethanol, propanol, 2-propanol, ethylene glycol Alcohols such as diethyl ether, tetrahydrofuran and diphenyl ether, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride, pentane and n-hexane And aliphatic hydrocarbons. These solvents may be used alone or as a mixture of two or more thereof.

  The reaction temperature can be set to any temperature from −60 ° C. to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually arbitrary in the range of 5 minutes to 100 hours. Can be set.

Moreover, Formula (8-8) [In formula, R ^<16c >, R ^{< 50} >, R ^{< 60} >, R ^{< 61} > and t represent the same meaning as the above. The compound represented by formula (8-9) [wherein R ^11b represents the same meaning as described above] according to the method described in International Publication No. 2007/026221. The compound represented by Formula (8-5) can also be obtained by making it react with the compound represented by this.

Next, the compound represented by the formula (8-5) is subjected to a hydrolysis reaction according to a known method known in the literature, whereby the formula (8-6) [wherein R ^11b , R ^16c , R ⁶⁰ , R ⁶¹ and t represent the same meaning as described above. The compound represented by this can be obtained.

Subsequently, by reacting the compound represented by the formula (8-6) with a halogenating agent such as thionyl chloride or oxalyl chloride according to a known method known in the literature, the compound represented by the formula (8-7) [in the formula, R ^11b , R ^16c , R ⁶⁰ , R ⁶¹ and t have the same meaning as described above. The compound represented by this can be obtained.

  Reaction formula 8

Formula (8-8) [wherein R ^16c , R ⁵⁰ , R ⁶⁰ , R ⁶¹ and t represent the same meaning as described above. The compound represented by formula (8-10) [wherein R ^13b and R ^14b represent the same meaning as described above, according to the method described in International Publication No. 2009/102997 and the like. By reacting with the compound represented by formula (8-12), R ^13b , R ^14b , R ^16c , R ⁵⁰ , R ⁶⁰ , R ⁶¹ and t have the same meaning as described above. The compound represented by this can be obtained.

  Some of the compounds represented by formula (8-10) are known compounds, and some of them are commercially available. Others can be synthesized according to known methods described in the literature.

In addition, Formula (8-11) [wherein R ^13b , R ^14b , R ⁵⁰ , which can be synthesized by a known method described in Journal of the Chemical Society Parkin Transactions 1 1981, Vol. 18, p. 9, etc. R ⁶⁰ , R ⁶¹ , J ^b and t represent the same meaning as described above. The compound represented by formula (8-12) may be synthesized by reacting the compound represented by formula (8-4) with the compound represented by formula (8-4) using the same method as in reaction formula 7. I can do it.

Subsequently, the compound represented by the formula (8-12) is reacted using the same method as in the reaction formula 7, whereby the formula (8-13) [wherein R ^13b , R ^14b , R ^16c , R ⁶⁰ , R ^61, and t represent the same meaning as described above. And a compound represented by formula (8-14): wherein R ^13b , R ^14b , R ^16c , R ⁶⁰ , R ⁶¹ and t have the same meaning as described above. The compound represented by the compound represented by this can be obtained.

  The compounds of the present invention are stored in warehouses, so-called agricultural pests that harm agricultural and horticultural crops and trees, so-called livestock pests that parasitize livestock and poultry, so-called sanitary pests that cause various adverse effects in the human living environment such as houses. It is possible to effectively control insects such as so-called stored grain pests that harm cereals and the like, and pests such as mites, crustaceans, molluscs, and nematodes that occur and harm in similar situations at low concentrations.

Specific examples of insects, mites, crustaceans, mollusks and nematodes that can be controlled using the compounds of the present invention include, for example, the wasp chestnut gall wasp (Dryocosmus kuriphilus), the Argentine ant Argentine ant (Linepithema humile), Gunmy ant Army ant (Eciton burchelli, E. schmitti), Japanese carpenter ant (Camponotus japonicus), Green ant Pharaoh ant (Monomorium pharaonis), Bulldog ant class Bulldog ant (Myrmecia spp.), Fire ant class fire spant (Soop) , Asian giant hornet (Vespa mandarina), Japanese yellow hornet (Vespa simillima), large bee Large rose sawfly (Arge pagana), pine bee European pine sawfly (Neodiprion sertifer), bb sawfly (Athalia infumata), turnip sawnip (Turnip sawfly) Hymenoptera insects such as Athalia rosae)
Pear leaf miner (Bucculatrix pyrivorella), tea leaf roller (Caloptilia theivora), golden leaf soy Apple leafminer (Phyllonorycter ringoniella), citrus leafminer (Phyllocnistis citrella), immobilized leaflet Persimmon fruit moth (Stathmopoda masinissa), Peach fruit moth (Carposina sasakii), Allium leafminer (Acrolepiopsis sapporensis), Yami leafminer (Acrolepiopsis suzukiella), Peach fruit moth (Pel fruit) ), Diamondback moth (Plutella xylostella), red stem borer (Chilo suppressalis), Shibatatsuga Bluegrass webworm (Parapediasia teterrella) Cabbage webworm (Hellula undalis), Rice leaf roller (Cnaphalocrocis medinalis), Yellow moth moth (Conogethes punctiferalis), Cotton moth (Diaphania indica), Mulberry pyras (Mulberry pyras) Ostrinia furnacalis), European corn borer (Ostrinia nubilalis), Azuki bean borer (Ostrinia scapulalis), Sorghum moth Lesser corn stalk borer (Elasmopalpus lignosellus), ella borer L Tree borer Peach tree borer (Synanthedon exitiosa), Cosca Shiba Cherry tree borer (Synanthedon hector), Kubiakasukashiba (Toleria romanovi), Iraga Oriental moth (Monema flavescens), Aura Iga (Parasa consocia), Hiloheira Oiraga (Parasa) lepida), Parasa siniea, Parana siniea, Artona martini, Illiberis pruni, Illiberis rotundata, Carpenter moth (Cossus insularis), Codlingmon lum, Cydia Fruit moth (Grapholita dimorpha), Oriental fruit moth (Grapholita molesta), Bean pod borer (Leguminivora glycinivorella), Bean podworm (Matsumuraeses phaseoli), Grapeberry moss (Grape berryite moth) Smaller tea tortrix (Adoxophyes honmai), Apple coconut oyster Summer fruit tortrix (Adoxophyes orana fasciata), Apple peach oyster Asiatic leafroller (Archips breviplicanus), Midareka kumamaki Apple tortrix (Archips fuscocupreanus) Oriental tea tortrix (Homona magnanima), Tobihamaki Dark fruit-tree tortrix (Pandemis heparana), Matsukareha Pine moth (Dendrolimus spectabilis), Tsukakareha Jananese hemlock caterpillar (Dendrolimus superans), Takekareha, Japanese bamboo thrix ha Euthrix potatoria, Oriental lappet (Gastropacha orientalis), Kunugia undans, Kunugia yamadai, Tomato hornworm (Manduca quinquemaculata), Tobacco hornworm (Alliga moth) cunea), Mulberry tiger moth (Lemyra imparilis), white flies (Eilema fuscodorsalis), black buckwheat (Eilema laevis), white moths udoconspersa), Swan moth (Sphrageidus similis), Gypsy moth (Lymantria dispar), White-spotted tussock moth (Orgyia thyellina), Rice green caterpillar (Naranga aenescens), Naranga aenescens leaf worm (Aedia leucomelas), mushroom Cabbage armyworm (Mamestra brassicae), Ayayoto Oriental armyworm (Pseudaletia separata), Japanese swordfish Lawn grass cutworm (Spodoptera depravata), Southern army worm Southern armyworm (ex armed worm) Fall army worm Fall armyworm (Spodoptera frugiperda), cotton leaf worm Cotton leafworm (Spodoptera littoralis), common cutworm (Spodoptera litura), giant bollworm (Helicoverpa armigera), tobacco moth Orienta l tobacco budworm (Helicoverpa assulta), tobacco bad worm Tobacco budworm (Heliothis virescens), American tobacco moth Corn earworm (Helicoverpa zea), Japanese red moth Black cutworm (Agrotis ipsilon), Kaburaya moth Turnip moth (Agrotis segetum) ), Honey beetle Threespotted plusia (Ctenoplusia agnata), soy bean looper, soybean looper (Pseudoplusia includens), nettle cabbage cabbage looper (Trichoplusia ni), mugwort Japanese giant looper (Ascotis selenaria), brass white white butterfly Lis , Lepidoptera (Lepidoptera) such as Cabbage white butterfly (Pieris rapae crucivora), Ichimongiseri Straight swift (Parnara guttata), cotton leaf worm cotton leafworm (Alabama argillacea), sugarcane borer (Diatraea sacharalis) Insect,
The fruit fly Melon fly (Bactrocera cucurbitae), the fruit fly Oriental fruit fly (Bactrocera dorsalis), the Queensland fruit fly Queensland fruit fly (Bactrocera tryoni), the fruit fly Japanese orange fly (Bactrocera tsuneonis), the Mediterranean fruit fly Mediterraneitis fly (Anastrepha ludens), ring-fly fly Apple maggot (Rhagoletis pomonella), rice leaf fly Rice leaf miner (Agromyza oryzae), leaf flyer Pea leaf miner (Chromatomyia horticola), oil leaf fly Cabbage leafminer (Liriomyza brassicae) ), Green leaf fly Stone leek leafminer (Liriomyza chinensis), green leaf fly Pea leafminer (Liriomyza huidobrensis), tomato leaf fly Tomato leafminer (Liriomyza sativae), bean leaf fly Serpentine leafminer (Liriom yza trifolii), Japanese fruit fly (Drosophila suzukii), Small leaf rice leaf miner (Hydrellia griseola), Tsetse fly (Glossina morsitans, G. palpalis), White fly, Forest fly (Hippobca) Melophagus ovinus), Onion fly (Delia antiqua), Seed corn maggot (Delia platura), sugar beet fly, Beet leaf miner (Pegomya cunicularia), Lesser house fly (Fannia canicularis), Sheep head fly (Hritae flyfly) ), Sweet fly (Morellia simplex), Face fly (Musca autumnalis), Housefly (Musca domestica), Australian bush fly (Musca vetustissima), Horn flies Horn fly (Haematobia irritans), Stable fly (Stable fly) Stomoxys calci trans, Calliphora lata, Bottle fly (Calliphora vicina), Old world screw-worm fly (Chrysomya bezziana), Blow fly (Chrysomya chloropyga), Oriental latrine fly (Chrysomya, Chrysomya America) New World screw-worm fly (Cochliomyia hominivorax), Black blow fly (Phormia regina), Northern blowfly (Protophormia terraenovae), sheep fly, Australian sheep blowfly (Lucilia cuprina), Green bottle fly (Lucilia illustris) Common green bottle fly (Lucilia sericata), Bot flies (Cuterebra spp.), Human fly botfly (Dermatobia hominis), Horse-nosed bot fly (Gasterophilus haemorrhoidalis), Horse-fly Horis bottest t fly (Gasterophilus nasalis), Bullflies Warble fly (Hypoderma bovis), Common cattle grub (Hypoderma lineatum), Sheep nasal bot fly (Oestrus ovis), Fresh fly Flesh fly (Sarcophaga carnaria), perch Srina ), Splayed deerfly (Chrysops caecutiens), Mekurabu Deer fly (Chrysops suavis), Common horse fly (Haematopota pluvialis), Greenhead horsefly (Greenhead horse fly (Tabanus nigrovittatus)) ), Soybean pod gall midge (Asphondylia yushimai), Hessian fly Hessian fly (Mayetiola destructor), mud wings Orange wheat blossom midge (Sitodiplosis mosellana), chick nuka Biting midge (Culicoides arakawae), L nipponens is), Black-tailed Blackfish (Prosimulium yezoensis), Black fly (Simulium ochraceum), African Malaria mosquito (Anopheles gambiae), Red-backed Shrimp (Anopheles hyrcanus sinesis), Anophelestosi aegypti), Asian tiger mosquito (Aedes albopictus), Chikaeka House mosquito (Culex pipiens molestus), Akaieka House mosquito (Culex pipiens pallens), Culex tritaeniorhynchus, moth P Diptera insects such as Telmatoscopus albipunctatus)
Chicken flea Hen flea (Ceratophyllus gallinae), Japanese flea Chigoe flea (Tunga penetrans), Dog flea Dog flea (Ctenocephalides canis), Cat flea Cat flea (Ctenocephalides felis), Chicken flea Sticktight flea (Echidnopha human ritual) , Siphonaptera insects such as Oriental rat flea (Xenopsylla cheopis),
Tobacco beetle (Lasioderma serricorne), Common bean weevil (Acanthoscelides obtectus), Adzuki bean beetle (Callosobruchus chinensis), Grape borer (Xylotrechus pyrrhoder beetle beetle) White-spotted longicorn beetle (Anoplophora malasiaca), Japanese pine sawyer (Monochamus alternatus), Yellow-spotted longicorn beetle (Psacothea hilaris), Colorado potato beetle Colorado beetle beetle (Phaedon cochleariae), rice leaf beetle Rice leaf beetle (Oulema oryzae), spotted leaf beetle (Demotina fasciculata), leaf beetle Cucurbit leaf beetle (Aulacophora femoralis) Beet flea beetle (Chaetocnema concinna), Northern corn rootworm (Diabrotica barberi), Southern corn rootworm (Diabrotica undecimpunctata), Western corn rootworm Western corn rootworm (Diabrotica virgifera), Triped P flea beetle striolata), Solanum flea beetle (Psylliodes angusticollis), green beetle Mexican been beetle (Epilachna varivestis), large twenty-eight-spotted ladybird (Epilachna vigintioctomawata bird), (Epilachna vigintioctopunctata), Epuraea domina, Pollen beetle (Meligethes aeneus), Peach curculio (Rhynchites heros), Sweetpotato weevil (Cylas formicarius), potato weevil West Indian sweet potato weevil (Euscepes postfasciatus), cotton weevil Boll weevil (Anthonomus grandis), white-flying beetle White-fringed beetle (Graphognatus leucoloma), horned weevil weevil Octopus weevil Alfalfa weevil (Hypera postica), Granary weevil (Sitophilus granarius), Chinese weevil Maize weevil (Sitophilus zeamais), Shibao weevil Hunting billbug (Sphenophorus venatus vestitus), Ezo weevil weevil (Lissohoptrus oryzophilus), yellow mealworm (Tenebrio molitor), red flour beetle (Tribolium castaneum), sweet potato wireworm (Melanotus fortnumi), citrus fruit Tsuruga Sugarcane wireworm (Melanotus tamsuyensis), Coreus crested citrus flower chafer (Gametis jucunda), Nagachakogane, Yellowish elongate chafer (Heptophylla picea), Douganebuibu Cupreous chafer (Anomala cuprea), Japanese beetle ), Coleoptera insects such as Rove beetle (Paederus fuscipes),
Asian citrus psyllid (Diaphorina citri), pear sucker Pear sucker (Psylla pyrisuga), Chatel spiny whitefly (Aleurocanthus camelliae), orange spiny whitefly (Aleurocanthus spiniferus), white leaffly (Aleurocanthus spiniferus) Whitefly Sweetpotato whitefly (Bemisia tabaci), Citrus whitefly (Dialeurodes citri), Greenhouse whitefly (Trialeurodes vaporariorum), Pea aphid (Acyrthosiphon pisum), Bean accura bee crab aphid (Aphis fabae), Soybean Aphid (Aphis glycines), Cotton Aphid (Aphis gossypii), Apple Aphid (Aphis pomi), Spiraea aphid (Aphis pomi) Aphis spiraecola), Foxglove aphid (Aulacorthum solani), Leaf curl plum aphid (Brachycaudus helichrysi), Japanese aphid Cabbage aphid (Brevicoryne brassiae), Walnut aphid Wola Russian wheat aphid (Diuraphis noxia), plantain beetle Rosy apple aphid (Dysaphis plantaginea), peach beetle Mealy plum aphid (Hyalopterus pruni), black pea aphid Turnip aphid (Lipaphis erysimi), tulip beetle aphid Margin door aphid (Monellia caryella), peach aphid Green peach aphid (Myzus persicae), Lettuce aphid (Nasonovia ribisnigri), Nephia Onion aphid (N eotoxoptera formosana), wheat cherry-oat aphid (Rhopalosiphum padi), rice aphid Rice root aphid (Rhopalosiphum rufiabdominalis), wheat leaf aphid (Sitobion akebiae), English grain aito avenae), Greenbug (Schizaphis graminum), Black citrus aphid (Toxoptera aurantii), Brown citrus aphid (Toxoptera citricida), Apple weevil Wooly apple aphid (Eriosoma lanigerum), Grape aphid Viteus vitifolii), hornet beetle Indian wax scale (Ceroplastes ceriferus), ruby weevil Red wax scale (Ceroplastes rubens), citrus scale insect (Coccus pseudomagnoliarum), red beetle California red scale (Aonidiella aurantii), pear Scale scale San jose scale (Comstockaspis perniciosa), scale scale tea scale (Teori scale), scale scale scale Peony scale (Pseudaonidia paeoniae), scale beetle scale Mulberry scale (Pseudaulacaspis pentagona), white scale scale Pula scale pi Citrus snow scale (Unaspis citri), Euonymus scale (Unaspis euonymi), Agarhead scale (Unaspis yanonensis), Giant margarodid scale (Drosicha corottenta scale) purchasi), worm beetle Cotton mealy bug (Phenacoccus solani), citrus mealybug (Citrus mealybug (Planococcus citri)), Japanese mealybug (Planococcus kuraunhiae), stag beetle Comstock me alybug (Pseudococcus comstocki), grape mealybug (Pseudococcus maritimus), brown brown planthopper (Laodelphax striatella), brown rice planthopper (Nilaparvata lugens), white-backedella planta (Gifer) Leafhopper (Epiacanthus stramineus), Indian cotton leafhopper (Amrasca devastans), Greens leafhopper (Bardsley leafhopper (Balclutha saltuella)), Aster leafhopper (Macrosteles fascifrons), Green leafy leafhopper (Macrosteles striifrons) leafhopper (Nephotettix cincticeps), Grape Leafhopper (Arboridia apicalis), Potato Leafhopper (Empoasca fabae), Emporasca nipponica, Chanomi Green leafhopper (Empoasca onukii), Bean's smaller green leafhopper (Empoasca sakaii), Sleek bug (Dolycoris baccarum), Sea turtle Cabbage bug (Eurydema rugosa), Spined whitespot ), White-spotted stink bug (Eysarcoris lewisi), white-spotted stink bug (Eysarcoris ventralis), blue-headed stink bug Sheild bug (Glaucias subpunctatus), brown marmorink stink bug (Halyomorpha haly) Nezara antennata), Southern green stink bug (Nezara viridula), Redbanded stink bug (Piezodorus guildinii), Redbanded shield bug (Piezodorus hybneri), Brown-winged crossota (Brown-winged cross bug) Japanese black rice bug (Scotinophora lurida), Bean bug (Riptortus clavatus), Spider helicopter Rice bug (Leptocorisa chinensis), Japanese stink bug Rice stink bug (Cletus punctiger), Southern bug shrimp bug (Paradasynus spinosus), Red-backed Helicopod Bug Rhopalid bug (Rhopalus maculatus), American Red-footed Beetle True chinch bug (Blissus leucopterus), Japanese Red-headed Bug, Oriental chinch bug (Cavelerius saccharivorus) Red cotton bug (Dysdercus cingulatus), Venezuelan sand turtle Blood-sucking bug (Rhodnius prolixus), Mexican sand turtle Kissing bug (Triatoma dimidiata), Brazilian sand turtle Kissing bug (Triatoma infestans), green stink bug sternumhil Aster ), Blown Stink bag brown stink bug (Euschistus servus), Southern green stink bag (Nezara viridula), Tarnished plant bug (Lygus lineolaris), Stink bag (Dichelops furcatus), Sugarcans pitle bag sugarcane spittlebug (Mahanarva fimbriolata), azalea lace bug (Stephanitis pyrioides), bed bug Bed bug (Cimex lectularius), bluefin turtle Pale greenplant bug (Apolygus spinolae), western tarnished plant bug (Lygus hesperus) Tarnished plant bug (Lygus lineolaris), Nagamushikasikameka Rice stink bug (Stenodema sibiricum), Akasujikasikameka Sorghum plant bug (Stenotus rubrovittatus), Rice fossil turtle Rice leaf bug (Trigonotylus caelestlium) Hemiptera insects such as and fleahopper (Halticus insularis), Cotton fleahopper (Pseudatomoscelis seriatus), Flower thrips (Frankliniella intonsa), Green lizard Yellow tea thrips (Scirtothrips dorsalis), Southern thrips Melon thrips (Thrips palmi), Black thrips Onion thrips (Thrips tabaci), Japanese gall-forming thrips (optonicthrips) ,
Chick shaft louse (Menopon hallid) (Cuclotogaster heterographa), brown fin louse (Goniodes dissmilis), bluefin louse Fluff louse (Goniodes gallinae), large bald larvae Large hen louse (Goniodes gigas), chicken swallow louse (Duru) ), Cat louse Cat louse (Felicola subrostrata), dog lice Dog biting louse (Trichodectes canis), cattle lice Short-nosed cattle louse (Haematopinus eurysternus), cattle lice Tail switch louse (Haematopinus quadripertusus), pig louse L inus suis), buffalo louse (Haematopinus tuberculatus), dog lice Dog sucking louse (Linognathus setosus), bovine white lice Long-nosed cattle louse (Linognathus cattle louse (Haemodipsus ventricosus ), Human louse Head louse (Pediculus humanus), mouse louse Mouse louse (Polyplax serratus), pheasant Crab louse (Pthirus pubis), etc.
Desert locust (Schistocerca gregaria), Australian platypus locust Australian plague locust (Chortoicetes terminifera), locust grasshopper Migratory locust (Locusta migratoria), red-eye locust Lesser paddy grasshopper (Oxya japonica), red-eye grass oxen (Teleogryllus emma), Kela Oriental mole cricket (Gryllotalpa orientalis), etc., Orthoptera insects,
German cockroach (Blattella germanica), American cockroach (Periplaneta americana), Black cockroach Smoky-brown cockroach (Periplaneta jafonica), Japanese cockroach (Periplaneta japonica), Daikokuus tomato (America) Termite Western dry-wood termite (Incisitermes minor), Common termite Formosan subterranean termite (Coptotermes formosanus), Japanese termite Japanese subterranean termite (Reticulitermes speratus), Thai termite Black-winged subterranean termite (Odontotermes formosanus) ,
Rootfeeding springtail (Onychiurus folsomi), Siberian white beetle (Onychiurus sibiricus), Garb spring spring (Bourletiella hortensis), etc.
Isopoda crustaceans such as Pill bug (Armadillidium vulgare), common rough woodlouse (Porcellio scaber),
Butterflyfish (Arguloida) crustaceans such as butterfly (Argulus coregoni), butterfly Japanese fishlouse (Argulus japonicus), sea butterfly (Argulus scutiformis)
Sea louse (Caligus curtus, C. elongatus), Salmon rose Salmon louse (Lepeophtheirus salmonis) and other crustaceans (Siphonostomatoida) crustaceans,
Sayaashi mite Storage mite (Glycyphagus destructor), house ticks mite (Glycyphagus domesticus), wheat mite Brown-legged grain mite (Aleuroglyphus ovatus), black mite Cheese mite (Tyrophagus putrescentiae), spiny mite Tyrophas , Hyugata mite Feather mite (Pterolichus obtusus), chick mite Feather mite (Megninia cubitalis), white house mite American house dust mite (Dermatophagoides farinae), yellow leopard mite bovis), Dog ear mite (Otodectes cynotis), Cattle cypress mite Psoroptic mite (Psoroptes communis), Rabbit ear mite Rabbit ear mite (Psoroptes cuniculi), Sheep cucumber Nhizendani Sheep scab mite (Psoroptes ovis), SENKOU mites Itch mite (Sarcoptes scabiei), cat foraminous mites Cat mange mite (Notoedres cati) mites suborder such as (Astigmata) mites,
Orabatida mites, such as the house salad ni (Haplochthonius simplex)
Sperm tick (Chelacaropsis moorei), cat tick (Cheyletiella blakei), rabbit tick Rabbit fur mite (Cheyletiella parasitovorax), crested tick (Cheyletiella yasguri), crested tick (Cheyletus eruditus), tick mite (Cheyletus eruditus) ), Caterpillar mites Cat follicle mite (Demodex cati), Acne mites Face mite (Demodex folliculorum), Tulip rust mites Wheat curl mite (Aceria tulipae), Black rust mites Pear rust mite (Eriophyes chibaensis), Peach bud insi ), Pearleaf blister mite (Eriophyes pyri), tea rust mite Tea rust mite (Acaphylla theavagrans), tomato rust mite Tomato russet mite (Aculops lycopersici), citrus mite Pink citrus rust mite (Aculops pelekassi) e rust mite (Aculus schlechtendali), Citrus rust mite Citrus rust mite (Phyllocoptruta oleivora), mite broad mite (Polyphagotarsonemus latus), cyclamen mite Cyclamen mite (Phytonemus pallidus), chuone mus mite Mite spider mite Citrus red mite (Panonychus citri), Mite spider mite Spider mite (Panonychus mori), Apple spider mite European red mite (Panonychus ulmi), Kanzawa spider mite Kanzawa spider mite (Tetranychus kanzawai), Nami spider mite Two mite Two-spot mite erythrocephalus), wheat mite Winter grain mite (Penthaleus major), Etsurombicula wichmanni, Miyagata pine tsutsumugi Trombiculid mite (Helenicula miyagawai), red tsutsugamushi (Leptotrombidium akamushi), yellow tsutsugamushi Prostigmata mites, such as Leptotrombidium pallida, Tsutsutsugamushi mite (Leptotrombidium scutellare),
English fowl tick (Argas persicus), tick soft tick (Ornithodoros moubata), relapsing fever tick (Ornithodoros turicata), spinose ear tick (Otobius megnini), Lone star tick (Lone star tick) Amblyomma americanum, Gulf coast tick (Amblyomma maculatum), Tick tick (Haemaphysalis campanulata), Tick tick (Haemaphysalis flava), Bite tick (Haemaphysalis longicornis), Mega physic tick (Haemaphysalis longicornis) aegyptium), Mediterranean tick (Hyalomma marginatum), Tropical cattle tick (Boophilus microplus), Ixodes nipponensis, Yamato tick (Ixodes ovatus), Western black-legge d tick (Ixodes pacifcus), Schulze tick Taiga tick (Ixodes persulcatus), Sheep tick Castor bean tick (Ixodes ricinus), Black-legged tick (Ixodes scapularis), Tropical horse tick (Anocentor nitens), Rocky Mountains Rocky Mountain wood tick (Dermacentor andersoni), Pacific Coast tick (Dermacentor occidentalis), Amikemeka tick Ornate cow tick (Dermacentor reticulatus), American dog tick American dog tick (Dermacentor variabilis), Ripicentor spp. Tick American cattle tick (Rhipicephalus annulatus), Brown dog tick (Rhipicephalus sanguineus) and other ticks (Metastigmata) ticks,
Red mite (Dermanyssus gallinae), house dust mite Tropical rat mite (Ornithonyssus bacoti), northern fowl mite (Ornithonyssus sylviarum), honey bee mite Honeybee mite (Varroa destructor), honeybee mite Varroa mite Varroa mite (Mesostigmata) mites,
Pancreas (Architaenioglossa) gastropod, such as Apple snail (Pomacea canaliculata)
Giant African snail (Achatina fulica), terrestrial slug (Limax marginatus), slug slug (Meghimatium bilineatum), Korean round snail (Acusta despecta sieboldiana), Miss maimai Land snio (Euhadra mai) Eyes (Stylommatophora) gastropods,
Giant kidney worm (Dioctophyma renale), ringed capillary worm Thread worms (Capillaria annulata), torsion capillary nematode Cropworm (Capillaria contorta), liver capillary nematode Capillary liver worm (Capillaria hepatica), penetrating capillary nematode (Capillaria) perforans), Philippine Capillaria philippinensis, Capillaria suis, Caterpillar Whipworm (Trichuris discolor), Whipworm Whipworm (Trichuris ovis), Pig whipworm Pig Whipworm (Trichuris suis), human Enoplida nematodes such as the whipworm Human whipworm (Trichuris trichiura), dog whipworm Dog whipworm (Trichuris vulpis), Trichinella pork worm (Trichinella spiralis),
桿 such as Nipple faecal nematode Intestinal threadworm (Strongyloides papillosus), cat fecal nematode (Strongyloides planiceps), pig fecal nematode Pig threadworm (Strongyloides ransomi), human fecal nematode Threadworm (Strongyloides stercoralis), Micronema spp. Rhabditida nematode,
Brazilian Hookworm (Ancylostoma braziliense), Dog Hookworm Dog hookworm (Ancylostoma caninum), Zubini Hookworm Old World hookworm (Ancylostoma duodenale), Cat Hookworm Cat hookworm (Ancylostoma tubaeforme), Narrowhead Hookworm The Northern hookworm of dogs (Uncinaria stenocephala) Caterpillar Cattle hookworm (Bunostomum phlebotomum), Sheep worm, Small ruminant hookworm (Bunostomum trigonocephalum), American worm New World hookworm (Necator americanus), Cyathostomum spp., Cylicocyclus spyl. spp.), Cylicostephanus spp., Donkeys (Strongylus asini), edentulous (Strongylus edentatus), Horse worms Blood worm (Strongylus equinus), Common worms Blood worm (Strongylus vulgaris) Large-mouthed bowel worm (Chabertia ovina), Indian nodular worm (Oesophagostomum brevic) audatum), Colombian nodule worm (Oesophagostomum columbianum), Nodule worm (Oesophagostomum dentatum), Nodular worm (Oesophagostomum georgianum), Nodular worm (Oesophagostomum columbianum) Nodular worm (Oesophagostomum quadrispinulatum), cattle intestinal nodular worm (Oesophagostomum radiatum), goat intestinal nodular worm (Oesophagostomum venulosum), scrijabin worm (Syngamus skrjabinomorpha), chicken worm moth trachea (Syngamus skrjabinomorpha) Swine kidney worm (Stephanurus dentatus), Couperia cattle bankrupt worm (Cooperia oncophora), red stomach worm (Hyostrongylus rubidus), stomach hair worm (Trichostrongylus axei), serpentine ciliate nematode (Trichostrongylus colubriformis), Oriental ciliate nematode Oriental trichostrongylus (Trichostrongylus orientalis), torsion stomachworm Red stomach worm (Haemonchus co ntortus), cattle stomach worm (Mecistocirrus digitatus), Ostertag stomach worm (Ostertagia ostertagi), filamentous lungworm Common lungworm (Dictyocaulus filaria), bovine lungworm Bovine lungworm (Dictyocaulus viviparus) Insect worms (Nematodirus filicollis), Swine lungworm (Metastrongylus elongatus), Lungworm (Filaroides hirthi), Lungworm (Crenosoma aerophila), Fox lungworm (Crenosoma vulpis) Strong lungida nematodes such as Rat lung worm (Angiostrongylus cantonensis), Schistosoma nematode French heartworm (Angiostrongylus vasorum), Protostrongylus spp.
Rice white nematode (Aphelenchoides besseyi), Pine wood nematode (Bursaphelenchus xylophilus) nematode (Aphelenchida) nematode,
Potato cyst nematode (Globodera rostochiensis), wheat cyst nematode Cereal cyst nematode (Heterodera avenae), soybean cyst nematode (Seterbean cyst nematode (Heterodera glycines)), arenaria root nematode (Peterut root-Menot nematode) -knot nematode (Meloidogyne hapla), Southern root-knot nematode (Meloidogyne incognita), Java root-knot nematode (Meloidogyne javanica), Southern root-kion nematode Coffee root-lesion nematode (Pratylus nechade) Root-lesion nematode (Pratylenchus loosi), Cobb's root-lesion nematode (Pratylenchus penetrans), Crested nematode Walnut root-lesion nematode (Pratylenchus vulnus), etc. lenchida) nematode,
Oxyurida nematodes such as human worm Pinworm (Enterobius vermicularis), horse worm Equine pinworm (Oxyuris equi), rabbit worm Rabbit pinworm (Passalurus ambiguus),
Pig roundworm (Ascaris suum), Horse roundworm Horse roundworm (Parascaris equorum), Dog roundworm Dog roundworm (Toxascaris leonina), Dog roundworm Dog intestinal roundworm (Toxocara canis), Cat roundworm Feline roundworm (Toxocara cati), Cattle roundworm Large cattle roundworm (Toxocara vitulorum), Anisakis spp., Pseudoterranova spp., chicken caecal caecal worm (Heterakis gallinarum), chicken roundworm (Ascaridia galli) and other roundworms (Ascaridida) Nematode,
Medinaworm Guinea worm (Dracunculus medinensis), Dolores jaw-and-mouth beetle (Gnathostoma doloresi), Ganthostoma hispidum, Japanese jaw-and-mouth beetle (Gnathostoma nipponicum), Reddish-coloured worm (Gnathostoma spinigerum) Dog stomach worm (Physaloptera canis), cat stomach worm (Physaloptera felidis, P. praeputialis), lala gastroworm Feline / canine stomach worm (Physaloptera rara), oriental eyeworm Eye worm (Thelazia callipaeda), Bovine eyeworm (Thelazia rhodesi), Large mouth stomach worm (Draschia megastoma), Equine stomach worm (Habronema microstoma), Stomach worm (Habronema muscae), Beautiful esophagus Gullet worm ( Gongylonema pulchrum), Thick stomach worm (Ascarops strongylina), Parafilaria (Parafilaria bovicola), Parafilaria multipapillosa, Stephanofilaria okinawaensis), Bancroft filaria (Wuchereria bancrofti), Malay filamentous worm (Brugia malayi), Neck threadworm (Onchocerca cervicalis), Gibson filamentous worm (Onchocerca gibsoni), Cattle filarial worm (Onchocercer gautum) ), Convolvulus (Onchocerca volvulus), finger filamentous worm Bovine filarial worm (Setaria digitata), equine filamentous peritoneal worm (Setaria equina), papillary larva (Setaria labiatopapillosa), marshall filariae (Setaria marshalli), dog Spirurida nematodes, such as the dog heartworm (Dirofilaria immitis) and the African eye worm (Loa loa),
Bald worms such as Moniliformis moniliformis, Giant thorny-headed worm (Macracanthorhynchus hirudinaceus),
Artificial leaves such as Fish tapeworm (Diphyllobothrium latum), Diphyllobothrium nihonkaiense, Manson tapeworm (Spirometra erinaceieuropaei), Diplogonoporus grandis Eye (Pseudophyllidea) tapeworm,
Wire worms (Mesocestoides lineatus), striped worms Chicken tapeworm (Raillietina cesticillus), spiny cleft worm Fowl tapeworm (Raillietina echinobothrida), square tapeworm Chicken tapeworm (Raillietina tetragona), canine tapeworm (Taenia hydatigena), Canine tapeworm (Taenia multiceps), sheep worm Sheep measles (Taenia ovis), beetle tapeworm Dog tapeworm (Taenia pisiformis), striped beetle Beef tapeworm (Taenia saginata), striped worm Tapeworm (Taenia serialis) ), Rodentworm Pork tapeworm (Taenia solium), caterpillar Feline tapeworm (Taenia taeniaeformis), single tapeworm Hydatid tapeworm (Echinococcus granulosus), multi-budworm, small fox tapeworm (Echinococcus multilocularis), cat (Echinococcus oligarthrus), Vogel's crustacean (Echinococcus vogeli), reduced tapeworm Rat tapeworm (Hymenolepis diminuta), small tapeworm Dwarf tapeworm (Hymenolepis nana), crustacea double-pored dog tapeworm (Dipylidium ca ninum), cuneate tapeworms (Amoebotaenia sphenoides), funnel-like crustaceans (Choanotaenia infundibulum), quail crustaceans (Metroliasthes coturnix), crustacea Equine tapeworm (Anoplocephala magna), phytophyte crustacean Cecal tapeworm (Anoplocephala perfoliata), papillae Insects Dwarf equine tapeworm (Paranoplocephala mamillana), Benedenta worm Common tapeworm (Moniezia benedeni), expanded tapeworm Sheep tapeworm (Moniezia expansa), Stysia spp.
Striated insects (Pharyngostomum cordatum), Schistosoma haematobium, Schistosoma haematobium, Schistosoma japonicum, Schistosoma japonicum, Schistosoma mansoni, etc.
Echinostoma cinetorchis, Echinostoma hortense, Giant liver fluke (Fasciola gigantica), Liver common liver fluke (Fasciola hepatica), Fasciolopsis buski, Flat belly twin Echinostomida, such as Homalogaster paloniae,
Continental flukes (Dicrocoelium chinensis), moth-type flukes Lancet liver fluke (Dicrocoelium dendriticum), African moth-type flukes African lancet fluke (Dicrocoelium hospes), small pancreatic folds (Eurytrema coelomaticum), pancreatic folds Pancreatic fluke (Eurytrema pancreaticum) Paragonimus miyazakii, Paragonimus ohirai, Westermann Lung fluke (Paragonimus westermani), etc. Platimorchiida
Amphimerus spp., Liver fluke Chinese liver fluke (Clonorchis sinensis), Cat liver fluke Cat liver fluke (Opisthorchis felineus), Thai liver fluke Southeast Aasian liver fluke (Opisthorchis viverrini), Pseudamphistom spp .), Metrochis spp., Parametorchis spp., Malformed fluke (Heterophyes heterophyes), Metagonimus yokokawai, foregut fluke (Pygidiopsis summa), etc. Opisthorchiida) fluke,
Amoeba such as Entamoeba histolytica, E. invadens,
Futago Babesia (Babesia bigemina), Cattle Babesia bovis, Big Horse Babesia caballi, Dog Babesia canis, Cat Babesia felis, Gibson dog Babesia gibsoni, Large Piroplasma (Babesia ovata) ), Cytauxzoon felis, tropical piroplasmosis Tyleria (Theileria annulata), pseudocoastal fever Tyreria (Theileria mutans), small piroplasma (Theileria orientalis), east coast fever Tyrelia (Theileria parva), etc. Piroplasmida sporophytes,
Haemoproteus mansoni, chicken leucocytozone (Leucocytozoon caulleryi), Plasmodium falciparum, Plasmodium malariae, Plasmodium ovale, Plasmodium ovale Haemosporida spores such as Plasmodium vivax,
Caryospora spp., Eimeria acervulina, Eimeria bovis, Eimeria brunetti, Eimeria maxima, Eimeria necatrix, Eimeria necatrix Eimeria ovinoidalis, rabbit liver coccidium (Eimeria stiedae), chicken cecal coccidium (Eimeria tenella), dog isospora canis, feline isospora (Isospora felis), porcine isospora suis (Isospora suis), Tizeria aleni , Tyzzeria anseris, Tyzzeria perniciosa, Wenyonella anatis, Wenyonella gagari, Cryptosporidium canis, cat crypt Cryptosporidium felis, Cryptosporidium hominis, turkey Cryptosporidium meleagridis, Cryptosporidium muris, small Cryptosporidium parvco, sarcosis (Sarcocystis cruzi), Sarcocystis felis, Sarcocystis hominis, Sarcocystis miescheriana, Sarcocystis neurona, Sarcocystis colostis tenis S tenis Sarcocystis ovalis), Toxoplasma gondii, dog hepatozoon (Hepatozoon canis), cat hepatozoon (Hepatozoon felis), etc. cidiorida) spores,
Vestibuliferida ciliates, such as large intestine barantidium coli,
Histomanas meleagridis, Pentatrichomonas hominis, Trichomonas tenax and other Trichomonadida flagellates,
Dipromonads (Diplomonadida) flagellates such as Giardia intestinalis, Giardia muris, turkey hexamita (Hexamita meleagridis), Hexamita parva,
Leishmania donovani, Leishmania infantum, Leishmania major, Leishmania tropica, Trypanosoma brucei gambiense, Trypanosoma brucei cruise, Trypanosoma brucei rhodesi Examples include Trypanosoma cruzi, Trypanosoma equiperdum, Trypanosoma evansi, and Kinetoplastida flagellates. Pests and ectoparasites such as livestock, poultry and pets are not limited to these.

  Furthermore, the compound of the present invention is also effective against pests that have developed resistance to existing insecticides such as organophosphorus compounds, carbamate compounds, and pyrethroid compounds.

  That is, the compound of the present invention is composed of the order of mucous eyes (Coleoptera), reticulates (Roaches), straight moths (Grasshoppers), termites, common moths (Thrips), hemimorphs (stink bugs and leafhoppers). Eyes), Lepidoptera (Lepidoptera), Coleoptera (Coleoptera), Hymenoptera (Hymenoptera), Diptera (Flyidae), Islamic (Flea), Liceid, and other insects, ticks In addition, pests belonging to gastropods and nematodes can be effectively controlled at low concentrations. On the other hand, the compounds of the present invention are extremely useful with little adverse effect on mammals, fish, crustaceans and beneficial insects (beneficial insects such as bees and bumblebees, natural enemies such as honeybees, wasps, mistletoe flies, mosquitoes, and mites). Has features.

  When using the compound of the present invention, it is usually mixed with a suitable solid carrier or liquid carrier, and if desired, a surfactant, penetrant, spreading agent, thickener, antifreezing agent, binder, anti-caking agent. , Disintegrating agents, antifoaming agents, preservatives and anti-degradation agents, etc., and soluble concentrate, emulsion (emulsifiable concentrate), wettable powder, water-soluble powder, granular water Water dispersible granule, water soluble granule, suspension concentrate, concentrated emulsion, suspoemulsion, microemulsion, dustable powder ), Granule tablets, and emulsifiable gels, and can be put to practical use. Further, from the viewpoint of labor saving and safety improvement, the preparations of any of the above dosage forms can be provided by being enclosed in a water-soluble package such as a water-soluble capsule and a bag of a water-soluble film.

  Examples of the solid carrier include quartz, calcite, gypsum, dolomite, chalk, kaolinite, pyrophyllite, sericite, halosite, metahalosite, kibushi clay, glazed clay, porcelain stone, siegrite, and allophane. Natural minerals such as shirasu, kira, talc, bentonite, activated clay, acid clay, pumice, attapulgite, zeolite and diatomaceous earth, for example, calcined clay, perlite, shirasu balloon, vermiculite, attapulgus clay and calcined diatomaceous earth Baked products such as magnesium carbonate, calcium carbonate, sodium carbonate, sodium bicarbonate, ammonium sulfate, sodium sulfate, magnesium sulfate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and potassium chloride, such as glucose, fructose , And Sugars such as sugar and lactose, polysaccharides such as starch, powdered cellulose and dextrin, organic materials such as urea, urea derivatives, benzoic acid and benzoic acid salts, such as wood flour, cork flour, corn cobs, walnut shells and Examples include plants such as tobacco stalks, fly ash, white carbon (for example, hydrous synthetic silica, anhydrous synthetic silica, hydrous synthetic silicate, etc.) and fertilizers.

Examples of the liquid carrier include xylene, alkyl (C ₉ or C ₁₀ etc.) benzene, phenyl xylyl ethane and alkyl (C ₁ or C ₃ etc.) naphthalene and other aromatic hydrocarbons, machine oil, normal paraffin, isoparaffin and Aliphatic hydrocarbons such as naphthene, mixtures of aromatic and aliphatic hydrocarbons such as kerosene, alcohols such as ethanol, isopropanol, cyclohexanol, phenoxyethanol and benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, hexylene glycol , Polyhydric alcohols such as polyethylene glycol and polypropylene glycol, propyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol monomethyl ether, propylene glycol Ethers such as ethyl monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and propylene glycol monophenyl ether, ketones such as acetophenone, cyclohexanone and γ-butyrolactone, fatty acid methyl esters, dialkyl esters of succinic acid, dialkyl esters of glutamic acid, adipine esters such as dialkyl ester and dialkyl phthalate esters, N- alkyl (C _1, C ₈ or C _12, etc.) acid amide pyrrolidone, soybean oil, linseed oil, rapeseed oil, coconut oil, such as cottonseed oil and castor oil Examples include fats and oils, dimethyl sulfoxide and water.

  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 alkyl (mono or di) phenyl ether, polyoxyethylene (mono, di or tri) styryl phenyl ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene Ethylene fatty acid (mono or di) ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, castor oil ethylene oxide adduct, acetylene glycol, acetylene alcohol, ethylene oxide adduct of acetylene glycol, ethylene oxide adduct of acetylene alcohol and alkyl Nonionic surfactants such as glycosides, alkyl sulfate esters, alkylbenzene sulfonates, lignin sulfonates, alkyls Rufosuccinate, naphthalene sulfonate, alkyl naphthalene sulfonate, salt of formalin condensate of naphthalene sulfonic acid, salt of formalin condensate of alkyl naphthalene sulfonic acid, polyoxyethylene alkyl ether sulfate or phosphate ester salt, polyoxyethylene (Mono or di) alkyl phenyl ether sulfate or phosphate ester salt, polyoxyethylene (mono, di or tri) styryl phenyl ether sulfate or phosphate ester salt, polycarboxylate (eg polyacrylate, polymaleate and maleate) Copolymer of acid and olefin, etc.) and anionic surfactants such as polystyrene sulfonate, cationic surfactants such as alkylamine salts and alkyl quaternary ammonium salts, and amphoteric interfaces such as amino acid type and betaine type Sexual agents, silicone-based surfactants and fluorinated surfactants.

  The content of these surfactants is not particularly limited, but is usually preferably in the range of 0.05 to 20 parts by weight with respect to 100 parts by weight of the preparation of the present invention. These surfactants may be used alone or in combination of two or more.

  The application amount of the compound of the present invention varies depending on the application scene, application time, application method, cultivated crops, etc., but generally 0.005 to 50 kg per hectare (ha) is appropriate as the amount of active ingredient.

  On the other hand, when using the compound of the present invention for the control of the ectoparasites of mammals and birds as domestic animals and pets, an effective amount of the compound of the present invention is administered orally together with injection additives (intramuscular, Parenteral administration such as subcutaneous, intravenous, intraperitoneal; transdermal administration such as immersion, spraying, bathing, washing, pouring-on and spotting-on and dusting; nasal administration Can be administered. The compounds of the present invention can also be administered by molded products using strips, plates, bands, collars, ear marks, limb bands, labeling devices and the like. In administration, the compound of the present invention can be in any dosage form suitable for the administration route.

  Arbitrary forms to be prepared include solid preparations such as powders, granules, wettable powders, pellets, tablets, large pills, capsules, molded products containing active compounds; injection solutions, oral solutions, skin Liquid preparations used above or in body cavities; solution preparations such as Pour-on agents, spot-on agents, flowable agents and emulsions; semi-solid preparations such as ointments and gels.

  The solid preparation can be used mainly for oral administration or diluted with water for transdermal administration or environmental treatment. Solid preparations can be prepared by adding the active compound, if necessary, with adjuncts, mixing with appropriate excipients, and converting to the desired shape. Suitable excipients include, for example, inorganic substances such as carbonates, bicarbonates, phosphates, aluminum oxides, silicas, clays, and organic substances such as sugars, cellulose, crushed grains, and starches.

  Injection solutions can be administered intravenously, intramuscularly and subcutaneously. Injection solutions dissolve the active compound in a suitable solvent and, if necessary, solubilizers, acids, bases, buffer salts, antioxidants. And can be prepared by adding additives such as protective agents. Suitable solvents include water, ethanol, butanol, benzyl alcohol, glycerin, propylene glycol, polyethylene glycol, N-methylpyrrolidone and mixtures thereof, physiologically acceptable vegetable oils, synthetic oils suitable for injection, and the like. Examples of solubilizers include polyvinylpyrrolidone, polyoxyethylated castor oil, and polyoxyethylated sorbitan ester. Protecting agents include benzyl alcohol, trichlorobutanol, p-hydroxybenzoic acid ester and n-butanol.

  Oral solutions can be administered directly or diluted. It can be prepared in the same manner as an injectable solution.

  Flowables, emulsions, etc. can be administered directly or diluted transdermally or by environmental treatment.

  Solutions used on the skin can be administered by dripping, spreading, rubbing, spraying, spraying or applying by dipping (immersion, bathing or washing). These solutions can be prepared in the same manner as injection solutions.

  Pour-on and spot-on agents can be dripped or sprayed onto a limited area of the skin, so that the active compound can be immersed in the skin and act systemically . Drops and drop preparations can be prepared by dissolving, suspending or emulsifying the active ingredient in suitable skin-compatible solvents or solvent mixtures. If necessary, auxiliary agents such as surfactants, colorants, absorption promoting substances, antioxidants, light stabilizers and adhesives may be added.

  Suitable solvents include water, alkanol, glycol, polyethylene glycol, polypropylene glycol, glycerin, benzyl alcohol, phenylethanol, phenoxyethanol, ethyl acetate, butyl acetate, benzyl benzoate, dipropylene glycol monomethyl ether, diethylene glycol monobutyl ether, acetone, Methyl ethyl ketone, aromatic and / or aliphatic hydrocarbons, vegetable or synthetic oil, DMF, liquid paraffin, light liquid paraffin, silicone, dimethylacetamide, N-methylpyrrolidone or 2,2-dimethyl-4-oxy-methylene-1, 3-dioxolane is mentioned. Absorption enhancers include DMSO, isopropyl myristate, dipropylene glycol pelargonate, silicone oil, aliphatic esters, triglycerides and fatty alcohols. Antioxidants include sulfites, metabisulfites, ascorbic acid, butylhydroxytoluene, butylhydroxyanisole and tocopherol.

  The emulsion can be administered orally, transdermally or as an injection. In emulsions, active ingredients are dissolved in a hydrophobic phase or a hydrophilic phase, and this is further added with a suitable emulsifier, and if necessary, a colorant, an absorption promoting substance, a protective agent, an antioxidant, a light-shielding agent, a thickening substance, etc. Can be prepared by homogenizing with other phase solvents together with other auxiliary agents.

  As hydrophobic phase (oil), paraffin oil, silicone oil, sesame oil, almond oil, castor oil, synthetic triglyceride, ethyl stearate, di-n-butyryl adipate, hexyl laurate, dipropylene glycol pelargonate, branched chain Of a short fatty acid having a chain length and a saturated fatty acid having a chain length of C16 to C18, isopropyl myristate, isopropyl palmitate, capryl / caprate of a saturated fatty alcohol having a chain length of C12 to C18, isopropyl stearate, oleyl oleate Decyl oleate, ethyl oleate, ethyl lactate, waxy fatty acid ester, dibutyl phthalate, diisopropyl adipate, isotridecyl alcohol, 2-octyldodecanol, cetyl stearyl alcohol, oleyl alcohol It is.

  Examples of the hydrophilic phase include water, propylene glycol, glycerin, and sorbitol.

  Emulsifiers include nonionic interfaces such as polyoxyethylated castor oil, polyoxyethylated sorbitan monoolefin acid, sorbitan monostearate, glyceryl monostearate, polyoxyethyl stearate, alkylphenol polyglycol ether, etc. Activators; amphoteric surfactants such as disodium N-lauryl-β-iminodipropionate and lecithin; anions such as sodium lauryl sulfate, fatty alcohol sulfate ether, monoethanolamine salt of mono / dialkyl polyglycol orthophosphate Surfactants; cationic surfactants such as cetyltrimethylammonium chloride.

  Other adjuvants include carboxymethyl cellulose, methyl cellulose, polyacrylate, alginate, gelatin, gum arabic, polyvinyl pyrrolidone, polyvinyl alcohol, methyl vinyl ether, a copolymer of maleic anhydride, polyethylene glycol, wax, colloidal silica.

  Semi-solid preparations can be administered by application on the skin or spreading or introduction into body cavities. Gels can be prepared by adding sufficient thickener to a solution prepared as described above for an injectable solution to produce a clear material having an ointment-like consistency.

  Next, formulation examples of the preparation when the compound of the present invention is used are shown. However, the formulation examples of the present invention are not limited 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 parts Other examples include anti-caking agents and decomposition inhibitors.

〔emulsion〕
Compound of the present invention 0.1-30 parts Liquid carrier 45-95 parts Surfactant 4.9-15 parts Others 0-10 parts Others include, for example, spreading agents, decomposition inhibitors, and the like.

[Suspension]
Compound of the present invention 0.1 to 70 parts Liquid carrier 15 to 98.89 parts Surfactant 1 to 12 parts Others 0.01 to 30 parts Others include, for example, antifreezing agents and thickeners.

(Granule wettable powder)
Compound of the present invention 0.1 to 90 parts Solid carrier 0 to 98.9 parts Surfactant 1 to 20 parts Others 0 to 10 parts Others include, for example, binders and decomposition inhibitors.

[Liquid]
Compound of the present invention 0.01 to 70 parts Liquid carrier 20 to 99.99 parts Others 0 to 10 parts Other examples include antifreezing agents and spreading agents.

[Granule]
Compound of the present invention 0.01 to 80 parts Solid carrier 10 to 99.99 parts Others 0 to 10 parts Others include, for example, binders, decomposition inhibitors and the like.

[Dust]
Compound of the present invention 0.01 to 30 parts Solid support 65 to 99.99 parts Others 0 to 5 parts Other examples include a drift inhibitor and a decomposition inhibitor.

  Next, although the formulation example which uses this invention compound as an active ingredient is shown more concretely, this invention is not limited to these.

  In the following formulation examples, “parts” means parts by weight.

[Formulation Example 1] wettable powder Compound No.1-001 20 parts pyrophyllite 74 parts Solpol 5039 4 parts (mixture of nonionic surfactant and anionic surfactant: Toho Chemical Co., Ltd.) Product name)
Carplex # 80D 2 parts (Synthetic hydrous silicic acid: Shionogi & Co., Ltd. trade name)
The above is uniformly mixed and ground to obtain a wettable powder.

[Formulation Example 2] Milk Compound of the present invention No.1-001 5 parts Xylene 75 parts N-methylpyrrolidone 15 parts Solpol 2680 5 parts (mixture of nonionic surfactant and anionic surfactant: Toho Chemical Industry (Product name)
The above is uniformly mixed to obtain an emulsion.

[Formulation Example 3] Suspension Agent Compound No.1-001 25 parts Agrisol S-710 10 parts (Nonionic Surfactant: Kao Corporation trade name)
LUNOX 1000C 0.5 part (anionic surfactant: Toho Chemical Industries, Ltd. trade name)
Xanthan gum 0.2 parts water 64.3 parts After uniformly mixing the above, wet pulverize to make a suspension.

[Composition Example 4] Granule wettable powder Compound No.1-001 of the present invention 75 parts Hytenol NE-15 5 parts (anionic surfactant: trade name of Daiichi Kogyo Seiyaku Co., Ltd.)
Vanillex N 10 parts (anionic surfactant: Nippon Paper Industries Co., Ltd. trade name)
Carplex # 80D 10 parts (Synthetic hydrous silicic acid: Shionogi Pharmaceutical Co., Ltd. trade name)
After uniformly mixing and pulverizing the above, a small amount of water is added, stirred and mixed, granulated with an extrusion granulator, and dried to obtain a granulated wettable powder.

[Formulation Example 5] Granule Compound No. 1-001 of the present invention 5 parts Bentonite 50 parts Talc 45 parts After uniformly mixing and pulverizing the above, a small amount of water is added and mixed with stirring, and granulated with an extrusion granulator. And dried into granules.

[Formulation Example 6] Powder Compound of the present invention No.1-001 3 parts Carplex # 80D 0.5 part (Synthetic hydrous silicic acid: Shionogi Pharmaceutical Co., Ltd. trade name)
Kaolinite 95 parts Diisopropyl phosphate 1.5 parts The above is uniformly mixed and ground to obtain a powder.

  In use, the above preparation is diluted 1 to 10000 times with water or sprayed directly without dilution.

[Formulation Example 7] wettable powder preparation Compound No. 1-001 of the present invention 25 parts sodium diisobutylnaphthalenesulfonate 1 part calcium n-dodecylbenzenesulfonate 10 parts alkylaryl polyglycol ether 12 parts naphthalenesulfonic acid formalin condensate Sodium salt 3 parts Emulsion type silicone 1 part Silicon dioxide 3 parts Kaolin 45 parts [Formulation Example 8] Water-soluble thickener preparation Compound No.1-001 20 parts Polyoxyethylene lauryl ether 3 parts Sodium dioctyl sulfosuccinate 3. 5 parts dimethyl sulfoxide 37 parts 2-propanol 36.5 parts [Formulation Example 9] Solution for spraying the present compound No.1-001 2 parts dimethyl sulfoxide 10 parts 2-propanol 35 parts acetone 53 parts [Formulation Example 10] transdermal Solution for administration The present compound No.1-001 5 Parts hexylene glycol 50 parts isopropanol 45 parts [Formulation Example 11] Solution for transdermal administration Compound No. 1-001 5 parts propylene glycol monomethyl ether 50 parts Dipropylene glycol 45 parts [Formulation example 12] transdermal administration (instillation) ) Solution for the Invention Compound No.1-001 2 parts Light Liquid Paraffin 98 parts [Formulation Example 13] Solution for the transdermal administration (drip) Compound No.1-001 2 parts Light Liquid Paraffin 58 parts Olive Oil 30 parts ODO -H 9 parts Shin-Etsu Silicone 1 part In addition, when the compound of the present invention is used as an agrochemical, other types of herbicides, various insecticides, acaricides, nematicides, You may mix and apply with a disinfectant, a plant growth regulator, a synergist, a fertilizer, a soil conditioner, etc.

  In particular, when mixed with other pesticides or plant hormones, the cost can be reduced by reducing the amount of applied medicine, the insecticidal spectrum can be expanded by the synergistic action of the mixed drugs, and higher pest control effects can be expected. At this time, a combination with a plurality of known agricultural chemicals is also possible. Examples of the type of agricultural chemical used in combination with the compound of the present invention include compounds described in The Pesticide Manual 15th edition, 2009, and the like. Specific examples of common names are as follows, but the general names are not necessarily limited to these.

  Bactericides: acibenzolar-S-methyl, acylaminobenzamide, acypetacs, aldimorph, ametoctradin, amisulbrom, amobam, ampropyl Phos (ampropyfos), anilazine, azaconazole, azithiram, azoxystrobin, barium polysulfide, benalaxyl, benalaxyl-M, benodaril (Benodanil), benomyl, benquinox, bentaluron, benthiavalicarb, benthiazole, benzamacril, benzamorf, bethoxazine, Binapacryl Biphenyl, bitertanol, blasticidin-S, bixafen, bordeaux mixture, boscalid, bromoconazole, bupirimate, buthiobate (Buthiobate), calcium polysulfide, calcium polysulfide, captafol, captan, carpropamid, carbamorph, carbendazim, carboxin (Carboxin), carvone, cheshunt mixture, chinomethionat, clobenthiazone, chloraniformethane, chloranil, chlorfenazol, Chloroneb (c hloroneb), chloropicrin, chlorothalonil, chlorquinox, chlozolinate, climbazole, clotrimazole, copper acetate, basic copper carbonate (copper carbonate, basic), cupric hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper sulfate, basic sulfuric acid Copper sulfate, basic, copper zinc chromate, cufraneb, cuprobam, cyazofamid, cyclafuramid, cycloheximide, cyflufenamid, Simoxanil, cypendazole, cyproconazole (cyp) roconazol), cyprodinil, cyprofuram, dazomet, debacarb, decaentin, dehydroacetic acid, dichlorfluanid, dichlone, Dichlorophen, dichlozoline, diclobutrazol, diclocymet, diclomedine, dicloran, etc.

  Bactericides (continued): diethofencarb, difenoconazole, diflumetorim, dimethirimol, dimethomorph, dimoxystrobin, diniconazole-M, diniconazole-M, diniconazole-M M), dinobuton, dinocap, dinocap-4, dinocap-6, dinoton, dinosulfon, dinoterbon, diphenylamine ), Dipyrithione, ditalimfos, dithianon, dodemorph, dodine, drazoxolon, edifenphos, epoxiconazole, etaconazole, etaconazole Xham (ethaboxam), etem, etirimol, ethoxyquin, etridianol, famoxadone, fenarimol, febuconazole, fenamidone, phenaminosulf ), Fenapanil, fendazosulam, fenfuram, fenhexamid, fenitropan, fenoxanil, fenpiclonil, fenpropidin, fenpyrazamine (fenpyrazamine), fenpropimorph, fentin, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, flumorph, full Fluopicolide, fluopyram, fluoroimide, fluotrimazole, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, fluthianyl (fluoxanil) flutianil), flutolanil, flutriafol, fluxapyroxad, folpet, fosetyl-aluminium, fuberidazole, fluralaxyl, flametopyr ( furametpyr), furcarbanil, furconazole, fluconazole-cis, furmecyclox, furphanate, furyonate, glyodin, griseofulvin, guazachi (Guazatine), halacrinate, hexachlorobenzene, hexaconazole, hexylthiofos, hydroxyquinoline sulfate, hymexazol, imazalil, Imibenconazole, iminoctadine, ipconazole, iprobenfos, iprodione, iprovalicarb, isoprothiolane, isovaledione, etc.

  Fungicide (continued): kasugamycin, kresoxim-methyl, mancopper, mancozeb, mandipropamid, maneb, mebenil, mecarbinzid , Mepanipyrim, mepronil, metalaxyl, metalaxyl-M, metam, metazoxolon, metconazole, metasulfocarb, metoxasulfocarb, metoxafloxam ), Methyl isothiocyanate, metiram, metinominostrobin, metrafenone, metsulfovax, milneb, microbutanil, microzoline (myclozo) lin), nabam, natamycin, nickel bis (dimethyldithiocarbamate), nitrostyrene, nitrothal-isopropyl, nuarimol, OH (OCH), octhilinone, offurace, orysastrobin, oxadixyl, oxine copper, oxycarboxin, oxpoconazole fumarate , Pefurzoate, penconazole, penflufen, penencycuron, penthiopyrad, o-phenylphenol, phosdiphen, phthalide, picoxis Robin (picoxystrobin), piperalin (piperalin), polycarbamate (polycarbamate), polyoxins (polyoxins), polyoxorim (polyoxorim), potassium azide (potassium hydrogen carbonate) (potassium hydrogen carbonate), proquinazid (proquinazid) probenazole), prochloraz, procymidone, propamocarb hydrochloride, propiconazole, propineb, prothiocarb, prothioconazole, pyracarbolid, Pyraclostrobin, pyrazophos, pyridinitril, pyrifenox, pyrimethanil, pyriofenone, pyroculone (pyroq) uilon, pyroxychlor, pyroxyfur, quinomethionate, quinoxyfen, quintozene, quinacetol-sulfate, quinazamid, quinazaazole, quinconazole rabenzazole).

  Fungicide (continued): sodium azide, sodium hydrogen carbonate, sodium hypochlorite, sulfur, spiroxamine, salicylanilide, silthiofam (Silthiofam), simeconazole, tebuconazole, tecnazene, tecoram, tetraconazole, thiabendazole, thiadifluor, thicyofen, thifluzamide thifluzamide, thiochlorfenphim, thiophanate, thiophanate-methyl, thioquinox, thiram, thiadinyl, tioxymid, tolcrophos-me Tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triamiphos, triarimol, triazoxide, triazbutil, tributyltin oxide ), Trichlamide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, validamycin, validamycin Examples include valifenalate, vinclozolin, zarilamide, zinc sulfate, zineb, ziram, zoxamide and shiitake mycelium extract.

  Bactericides: benzalkonium chloride, bithionol, bronopol, cresol, formaldehyde, nitrapyrin, oxolinic acid, oxyterracycline , Streptomycin and tecloftalam.

  Nematicides: aldoxycarb, cadusafos, DCP, DBCH, dichlofenthion, DSP (DSP), etoprophos, fenamiphos, fensulfothion, fluene Sulfone (fluensulfone), fosthiazate (fosthiazate), fosthietan (fosthietan), imisiafos (imicyafos), isamidofos (isamidofos), isazofos (isazofos), oxamyl (oxamyl) and thionazin (thionazin) and the like.

  Acaricide: acequinocyl, acrinathrin, amitraz, BCI-033 (test name), bifenazate, bromopropylate, chinomethionat, chlorobezilate , Clofentezine, cyenopyrafen, cyflumetofen, cyhexatine, dicofol, dienochlor, denochlor (DNOC), etoxazole, quinazaquin (fenaza) Fenbutatin oxide, fenothiocarb, fenpropathrin, fenpyroximate, fluacrypyrim, halfenprox (halfenpro) x), hexythiazox, milbemectin, propargite, pyflubumide, pyridaben, pyrimidifen, S-1870 (test name), spirodiclofen , Spyromesifen, CL900167 (test name) and tebufenpyrad.

  Insecticides: abamectin, acephate, acetamipirid, afidopyropen, alanidcarb, aldicarb, allethrin, azaphos-methyl (azmethiphos), azine-methyl- ), Bacillus thuringiensis, bendiocarb, benfluthrin, benfuracarb, bensultap, bifenthrin, bioallethrin, bioresmethrin, bioresmethrin (bistrifluron), buprofezin, butocarboxim, carbaryl, carbofuran, carbosulfan, cartap, chloranthranil Chlorantraniliprole, chlorethoxyphos (chlorethxyfos), chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos-methyl ), Chromafenozide, clothianidin, cyantraniliprole, cycloprothrin, cyflumetofen, cyfluthrin, beta-cyfluthrin, halothrin , Lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethr in), cyromazine, deltamethrin, diacloden, diafenthiuron, diazinon, dichlorvos, diflubenzuron, dimethylvinphos, dinotefuran ( dinotefuran, diofenolan, disulfoton, dimethoate, emamectin-benzoate, empenthrin, endosulfan, alpha-endosulfan, alpha-endosulfan, EPN, Esfenvalerate, ethiofencarb, ethiprole, etofenprox, etrimfos, fenitrothion, fenitrothion, Fenobucarb, fenoxycarb, fenpropathrin, fenthion, fenvalerate, fipronil, flonicamid, flubendiamide, flucythrinate ), Flufenerim, flufenoxuron, flufenprox, flumethrin, fluvalinate, tau-fluvalinate, fonophos, formethanate (Formetanate), formothion, furathiocarb, flufiprole, flupyradifurone, flometoquin and the like.

  Insecticides (continued): halofenozide, hexaflumuron, hydramethylnon, imidacloprid, isofenphos, indoxacarb, isoprocarb, isoxathion ), Lepimectin, lufenuron, malathion, meperfluthrin, metaflumizone, metalaldehyde, methamidophos, methidathion, methidathion, methacrifos (methacrifos) ), Metalcarb, methomyl, metoprene, methoxychlor, methoxyfenozide, methyl bromide , Monocrotophos, muscalure, nitenpyram, novaluron, noviflumuron, omethoate, oxamyl, oxydemeton-methyl, oxydemeton-methyl (oxydemeton-methyl) oxydeprofos, parathion, parathion-methyl, pentachlorophenol (PCP), permethrin, phenothrin, phenthoate, phoxim, phorate ), Phosalone, phosmet, phosphamidon, pirimicarb, pirimiphos-methyl, profenofos, prothiofos, propaphos, prototri Fenbut (protrifenbute), Pymetrozine (pymetrozine), Pyraclofos (pyraclofos), Pyrethrin (pyrethrins), Pyridalyl (pyrifluquinazon), Pyriprole (pyriprole), Pyrafluprole, Pyrifluprole (pyrifluprole) (Resmethrin), rotenone, SI-0405 (study name), sulprofos, silafluofen, spinetoram, spinosad, spirotetramat, sulfoxaflor , Sulfotep, SYJ-159 (test name), tebfenozide, teflubenzuron, tefluthorin, terbufos, tetrachlorvinphos, tetrameth Phosphorus (tetramethrin), dT-80-phthalthrin (d-tetramethrin), tetramethylfluthrin (tetramethylfluthrin), thiacloprid, thiocyclam, thiodicarb, thiamethoxam, thiophanox ( thiofanox, thiometon, tolfenpyrad, tralomethrin, trichlorfon, triazuron, triflumuron, vamidomion, ME-5382 (test name), ZDI2501 or NA- 89 etc.

  Hereinafter, the present invention will be described in more detail by specifically describing synthesis examples and test examples of the compounds of the present invention as examples, but the present invention is not limited thereto.

  The medium pressure preparative liquid chromatography described in the synthesis example used an intermediate pressure preparative apparatus (Yamazen Co., Ltd.); YFLC-Wprep (flow rate 18 ml / min, silica gel 40 μm column). Moreover, Shimadzu Corporation 10AVP system was used for the high performance preparative liquid chromatography.

Oven temperature: 40 ° C
Mobile phase: acetonitrile 7 ml / min, water 4 ml / min
Column: GL Science Inertsil-ODS3 (inner diameter 20 mm, length 250 mm, particle diameter 5 μm),
Measurement wavelength: 254 nm
Moreover, JASCO P-1020 was used for the measurement of the optical rotation.

[Synthesis example]
Synthesis example 1
Production of N- {3-chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -N-ethyl-2- (hydroxyimino) propanamide (present compound 1-003) Step 1
Preparation of tert-butyl 3-chloro-1- (pyridin-3-yl) -1H-pyrazol-4-ylcarbamate 3-chloro-1- (pyridin-3-yl) -1H-pyrazole-4-carboxylic acid 2 2.45 g of triethylamine and 2.00 g of diphenylphosphoryl azide were sequentially added to a 40 ml 2-methyl-2-propanol 20 ml solution at room temperature. After completion of the addition, the mixture was stirred for 4 hours while refluxing 2-methyl-2-propanol. After completion of the reaction, the reaction mixture was allowed to cool to room temperature, poured into ice water, and extracted with 50 ml of ethyl acetate. The obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane-ethyl acetate [1: 1 (volume ratio, the same shall apply hereinafter)] to obtain 0.86 g of the objective product as a white solid. Got as.
Melting point: 125-128 ° C.

Process 2
Preparation of tert-butyl 3-chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl (ethyl) carbamate
60% by weight sodium hydride (dispersed in mineral oil) 0.15 g of N, N-dimethylformamide solution in 10 ml of tert-butyl 3-chloro-1- (pyridin-3-yl) -1H- 0.95 g of pyrazol-4-ylcarbamate was added. After completion of the addition, the temperature was raised to room temperature and stirred at the same temperature for 30 minutes. After the completion of stirring, 0.55 g of ethyl iodide was added to the reaction mixture, and stirring was continued at room temperature for 1 hour. After completion of the reaction, the reaction mixture was poured into ice water and extracted with 100 ml of ethyl acetate. The obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane-ethyl acetate (2: 1) to obtain 1.06 g of the desired product as a yellow solid.
Melting point: 55-58 ° C
Process 3
Preparation of 3-chloro-N-ethyl-1- (pyridin-3-yl) -1H-pyrazol-4-amine dihydrochloride
tert-Butyl 3-chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl (ethyl) carbamate (1.0 g) in 1,4-dioxane (20 ml) was mixed with about 4 M hydrogen chloride in 1,4- 8.1 ml of dioxane solution was added. After completion of the addition, the mixture was stirred at room temperature for 12 hours. After completion of the reaction, the solid precipitated in the reaction solution was removed by filtration under reduced pressure. After drying under reduced pressure, 0.85 g of the desired product was obtained as a white solid.
Melting point: 132-133 ° C
Process 4
Preparation of 3-chloro-N-ethyl-1- (pyridin-3-yl) -1H-pyrazol-4-amine
To 7.4 ml of 1N aqueous sodium hydroxide solution, 1 g of 3-chloro-N-ethyl-1- (pyridin-3-yl) -1H-pyrazol-4-amine dihydrochloride was added. After completion of the addition, the mixture was stirred at room temperature for 3 hours. After completion of the reaction, the reaction mixture was extracted with dichloromethane (20 ml × 3). The obtained organic layer was dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to obtain 660 mg of the desired product as a white solid.
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 8.86 (d, J = 2.7 Hz, 1H), 8.46 (dd, J = 4.8, 1.2 Hz, 1H), 8.00-7.90 (m, 1H) 7.45 (ddd, J = 8.1, 4.8, 1.2 Hz, 1H), 7.33 (s, 1H), 3.01 (q, J = 7.2 Hz, 2H), 3. 00 (brs, 1H), 1.31 (t, J = 7.2 Hz, 3H)
Melting point: 89-90 ° C
Process 5
Preparation of N- {3-chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -N-ethyl-2-oxopropanamide
To a solution of 1 g of 3-chloro-N-ethyl-1- (pyridin-3-yl) -1H-pyrazol-4-amine in 10 ml of dichloromethane was added 0.59 g of pyruvic acid, 1-ethyl-3- (3- 1.7 g of (dimethylaminopropyl) carbodiimide hydrochloride and 3 mg of 4-dimethylaminopyridine were sequentially added. After completion of the addition, the mixture was stirred at the same temperature for 10 minutes. After completion of the reaction, 10 ml of water was added to the reaction mixture and extracted with 20 ml of dichloromethane. The obtained organic layer was dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane-ethyl acetate (1: 1) to obtain 1.4 g of the desired product as white crystals.
Melting point: 73-77 ° C
Step 6
Preparation of N- {3-chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -N-ethyl-2- (hydroxyimino) propanamide
N- {3-Chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -N-ethyl-2-oxopropanamide 400 mg of ethanol in 5 ml of solution was charged with 179 mg of triethylamine and 123 mg of hydroxylammonium chloride. Added. After completion of the addition, the mixture was stirred for 1 hour while refluxing ethanol. After completion of the reaction, the solvent was distilled off from the reaction mixture under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane-ethyl acetate (1: 1) to obtain 287 mg of the desired product as a white solid.
Melting point: 144-146 ° C
Synthesis example 2
Production of N- {3-chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -N-ethyl-2- (methylthiomethoxyimino) propanamide (present compound 1-001)
N- {3-Chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -N-ethyl-2- (hydroxyimino) propanamide 138 mg in N, N-dimethylformamide 1.5 ml solution 21.5 mg of 60 wt% sodium hydride (dispersed in mineral oil) was added under ice cooling. After completion of the addition, the mixture was stirred at the same temperature for 30 minutes. After completion of the stirring, 52 mg of chloromethyl methyl sulfide was added to the reaction mixture. After completion of the addition, stirring was continued for 5 hours at room temperature. After completion of the reaction, 5 ml of a saturated aqueous ammonium chloride solution was added to the reaction mixture, and the mixture was extracted with 30 ml of ethyl acetate. The obtained organic layer was washed with 10 ml of 1N sodium hydroxide aqueous solution and water 10 in this order, and then dehydrated and dried with saturated brine and then anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane-ethyl acetate (4: 1 to 1: 1 gradient) to obtain 77 mg of the desired product as a white solid.
Melting point: 92-95 ° C
Synthesis example 3
Production of N- {3-chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -2- (methoxyimino) -3- (methylthio) butanamide (present compound 1-057)
To a solution of 1.42 g of 2- (methoxyimino) -3- (methylthio) butanoic acid in 10 ml of dichloromethane was added 1.38 g of oxalyl chloride and then 10 mg of N, N-dimethylformamide at room temperature. After completion of the addition, the mixture was stirred at the same temperature for 2 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the resulting residue was separately prepared 3-chloro-N-ethyl-1- (pyridin-3-yl) -1H-pyrazol-4-amine 1 To a solution of .42 g and 1.44 g of pyridine in 20 ml of dichloromethane. After completion of the addition, the mixture was stirred at room temperature for 30 minutes. After completion of the reaction, the reaction solution was washed with 10 ml of water. The obtained organic layer was washed and dried in the order of saturated brine and then anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane-ethyl acetate (3: 1) to obtain 0.6 g of the desired product as a white solid.
Melting point: 80-82 ° C
Synthesis example 4
N- {3-chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -N- (cyanomethyl) -2- (methoxyimino) -3- (methylthio) butanamide (present compound 1 -056)
60% by weight of sodium hydride (dispersed in mineral oil) 54 mg of N, N-dimethylformamide in 5 ml of solution under ice-cooling, N- {3-chloro-1- (pyridin-3-yl) -1H-pyrazole- 400 mg of 4-yl} -2- (methoxyimino) -3- (methylthio) butanamide was added. After completion of the addition, the temperature was raised to room temperature and stirred at the same temperature for 1 hour. After stirring, 103 mg of chloroacetonitrile was added to the reaction mixture, and stirring was continued overnight at room temperature. After completion of the reaction, the reaction mixture was poured into ice water and extracted with 10 ml of ethyl acetate. The obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane-ethyl acetate (3: 1 to 1: 1 gradient) to obtain 120 mg of the objective product as a yellow amorphous.
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 8.93 (d, J = 2.7 Hz, 1H), 8.63 (dd, J = 4.8, 1.2 Hz, 1H), 8.20 (s, 1H), 8.01 (Ddd, J = 8.1, 2.7, 1.2 Hz, 1H), 7.46 (dd, J = 8.1, 4.8 Hz, 1H), 4.75 (d, J = 17.4 Hz) , 1H), 4.52 (d, J = 17.4 Hz, 1H), 4.12 (q, J = 7.2 Hz, 1H), 3.76 (s, 3H), 1.92 (s, 3H) ), 1.52 (d, J = 7.2 Hz, 3H)
Synthesis example 5
N- {3-Chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -N-ethyl-2- (methoxyimino) -3- (methylthio) butanamide (present compound 1-041 )Manufacturing of
To a solution of 0.4 g of 2- (methoxyimino) -3- (methylthio) butanoic acid in 5 ml of dichloromethane was added 0.39 g of oxalyl chloride and then 10 mg of N, N-dimethylformamide at room temperature. After completion of the addition, the mixture was stirred at the same temperature for 2 hours. After completion of the reaction, the solvent was distilled off under reduced pressure. The obtained residue was added to a solution of 0.46 g of 3-chloro-N-ethyl-1- (pyridin-3-yl) -1H-pyrazol-4-amine and 0.41 g of pyridine in 5 ml of dichloromethane prepared separately. . After completion of the addition, stirring was continued at room temperature for 30 minutes. After completion of the reaction, the reaction solution was washed with 10 ml of water. The obtained organic layer was washed and dried in the order of saturated brine and then anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane-ethyl acetate (3: 1) to obtain 0.35 g of the desired product as a white solid.
Melting point: 72-74 ° C
Synthesis Example 6
N- {3-Chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -N-ethyl-2- (methoxyimino) -3- (methylsulfinyl) butanamide (present compound 1- 042)
N- {3-chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -N-ethyl-2- (methoxyimino) -3- (methylthio) butanamide in a solution of 153 mg acetic acid in 3 ml At room temperature, 56 mg of 30 wt% aqueous hydrogen peroxide was added. After completion of the addition, the mixture was stirred at the same temperature for 12 hours. After completion of the reaction, 1 ml of a saturated aqueous sodium hydrogen sulfite solution was added to the reaction mixture, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography eluting with ethyl acetate-methanol (5: 1) to obtain 145 mg of the desired product as a colorless oil. The obtained target product was a mixture of two kinds of geometric isomers, and the isomer ratio was 3: 2.
Isomer ratio 3
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 8.93 (d, J = 2.7 Hz, 1H), 8.63-8.57 (m, 1H), 8.07-7.93 (m, 1H), 7.96 (s) , 1H), 7.44 (dd, J = 8.1, 4.8 Hz, 1H), 4.19-4.03 (m, 1H), 3.93-3.61 (m, 2H), 3 .75 (s, 3H), 2.57 (s, 3H), 1.51 (d, J = 7.2 Hz, 3H), 1.30-1.15 (m, 3H)
Isomer ratio 2
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 8.97 (d, J = 2.7 Hz, 1H), 8.58-8.53 (m, 1H), 8.15 (s, 1H), 8.07-7.93 (m , 1H), 7.40 (dd, J = 8.1, 4.8 Hz, 1H), 4.19-4.03 (m, 1H), 3.93-3.61 (m, 2H), 3 .72 (s, 3H), 2.58 (s, 3H), 1.49 (d, J = 7.2 Hz, 3H), 1.30-1.15 (m, 3H)
Synthesis example 7
N- {3-chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -N-ethyl-2- (methoxyimino) -3- (methylsulfonyl) butanamide (present compound 1- 002)
N- {3-Chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -N-ethyl-2- (methoxyimino) -3- (methylthio) butanamide in a solution of 158 mg of acetic acid in 3 ml of acetic acid At room temperature, 56 mg of 30 wt% aqueous hydrogen peroxide and 8 mg of sodium tungstate dihydrate were sequentially added. After completion of the addition, the mixture was stirred at the same temperature for 12 hours. After completion of the reaction, 1 ml of a saturated aqueous sodium hydrogen sulfite solution was added to the reaction mixture, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane-ethyl acetate (1: 1 to 0: 1 gradient) to obtain 160 mg of the desired product as a white solid. The obtained target product was a mixture of two geometric isomers, and the isomer ratio was 92: 8.
Isomer ratio 92
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 9.02-8.92 (m, 1H), 8.63-8.56 (m, 1H), 8.09 (s, 1H), 8.05-7.94 (m, 1H) ), 7.47-7.38 (m, 1H), 4.62 (q, J = 7.2 Hz, 1H), 3.95 (dq, J = 13.8, 6.9 Hz, 1H), 3 .77 (s, 3H), 3.56 (dq, J = 13.8, 6.6 Hz, 1H), 2.94 (s, 3H), 1.76 (d, J = 7.2 Hz, 3H) , 1.30-1.19 (m, 3H)
Isomeric ratio 8
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 9.02-8.92 (m, 1H), 8.63-8.56 (m, 1H), 8.09 (s, 1H), 8.05-7.94 (m, 1H) ), 7.47-7.38 (m, 1H), 4.90-4.78 (m, 1H), 3.95 (dq, J = 13.8, 6.9 Hz, 1H), 3.77. (S, 3H), 3.56 (dq, J = 13.8, 6.6 Hz, 1H), 3.02 (s, 3H), 1.76 (d, J = 7.2 Hz, 3H), 1 .30-1.19 (m, 3H)
Synthesis example 8
N- {3-Chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -2- (methoxyimino) -3- (methylthio) butanamide [present compound 1-057 (* 3) ]Manufacturing of
N- {3-Chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -2- (methoxyimino) -3- (methylthio) butanamide 3.0 g of acetic acid prepared in Synthesis Example 8 The 10 ml solution was stirred at the reflux temperature of acetic acid for 2 hours. After completion of the reaction, the solvent was distilled off under reduced pressure. The residue obtained after evaporation of the solvent was purified with a silica gel column of n-hexane: ethyl acetate = 7: 3 to obtain 0.3 g of the objective product as a yellow oil.
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 9.44 (brs, 1H), 8.98 (d, J = 2.4 Hz, 1H), 8.71 (s, 1H), 8.55 (dd, J = 4.8, 1 .2 Hz, 1H), 7.99 (ddd, J = 8.1, 2.4, 1.2 Hz, 1H), 7.39 (dd, J = 8.1, 4.8 Hz, 1H), 4. 17-4.01 (m, 1H), 4.09 (s, 3H), 2.10 (s, 3H), 1.52 (d, J = 7.2 Hz, 3H)
Synthesis Example 9
Ethyl 2-{(3-chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl) (methyl) amino} -N-methoxy-2-oxoethaneimidethioate (present compound 1- 078)
Process 1
Preparation of ethyl 2- (ethylthio) -2- (hydroxyimino) acetate
A solution of 1.0 g of ethyl 2-chloro-2- (hydroxyimino) acetate in 10 ml of N, N-dimethylformamide was cooled to 0 ° C., and 1.22 g of sodium ethyl mercaptan was added. After completion of the addition, the mixture was stirred at the same temperature for 1 hour. After completion of the reaction, 20 ml of water was added to the reaction solution and extracted with 20 ml of ethyl acetate. The obtained organic layer was washed with water, then washed and dried with saturated brine and then anhydrous sodium sulfate in this order, and the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane-ethyl acetate (3: 1) to obtain 0.95 g of the desired product as a colorless oil.
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 8.86 (brs, 1H), 4.34 (q, J = 7.2 Hz, 2H), 3.08 (q, J = 7.5 Hz, 2H), 1.36 (t, J = 7.2 Hz, 3H), 1.29 (t, J = 7.5 Hz, 3H)
Process 2
Production of ethyl 2- (ethylthio) -2- (methoxyimino) acetate
To a solution of 0.95 g of ethyl 2- (ethylthio) -2- (hydroxyimino) acetate in 10 ml of N, N-dimethylformamide, 1.85 g of potassium carbonate and 0.93 g of methyl iodide were sequentially added. After completion of the addition, the mixture was stirred at room temperature for 1 hour. After completion of the reaction, 10 ml of water was added to the reaction solution, followed by extraction with 10 ml of ethyl acetate. The obtained organic layer was washed with water, then washed and dried with saturated brine and then anhydrous sodium sulfate in this order, and the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane-ethyl acetate (10: 1) to obtain 0.66 g of the objective product as a colorless oil.
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 4.35 (q, J = 7.2 Hz, 2H), 4.07 (s, 3H), 3.00 (q, J = 7.5 Hz, 2H), 1.36 (t, J = 7.2 Hz, 3H), 1.27 (t, J = 7.5 Hz, 3H)
Process 3
Production of 2- (ethylthio) -2- (methoxyimino) acetic acid
To a solution of 0.66 g of ethyl 2- (ethylthio) -2- (methoxyimino) acetate in 5 ml of ethanol was added 4.1 ml of 1N aqueous sodium hydroxide solution. After completion of the addition, the mixture was stirred at room temperature for 30 minutes. After completion of the reaction, ethanol was distilled off from the reaction solution under reduced pressure. The resulting residue was adjusted to pH 2 by adding a 1N aqueous hydrochloric acid solution. After extraction with 5 ml (x2) of ethyl acetate, the extract was washed and dried with saturated brine and then anhydrous sodium sulfate in this order, and the solvent was distilled off under reduced pressure to obtain 0.12 g of the objective product as a colorless oil. (Contrast to isomerism ~ 3: 2).
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ
(Contrast 3) 3.95 (s, 3H), 2.80 (q, J = 7.5 Hz, 2H), 1.35 (t, J = 7.5 Hz, 3H)
(Isolation contrast 2) 3.48 (s, 3H), 2.97 (q, J = 7.2 Hz, 2H), 1.52 (t, J = 7.2 Hz, 3H)
Process 4
Preparation of ethyl 2-{(3-chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl) (methyl) amino} -N-methoxy-2-oxoethaneimidothioate
To a solution of 0.12 g of 2- (ethylthio) -2- (methoxyimino) acetic acid in 5 ml of dichloromethane was added 0.13 g of oxalyl chloride and then 10 mg of N, N-dimethylformamide at room temperature. After completion of the addition, the mixture was stirred at the same temperature for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure. The resulting residue was added to a separately prepared solution of 0.14 g of 3-chloro-N-methyl-1- (pyridin-3-yl) -1H-pyrazol-4-amine and 0.13 g of pyridine in 10 ml of dichloromethane. . After the addition was complete, stirring was continued overnight at room temperature. After completion of the reaction, the reaction solution was washed with 10 ml of water. The obtained organic layer was washed and dried in the order of saturated brine and then anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane-ethyl acetate (1: 1), and further purified using high speed preparative liquid chromatography to obtain the desired product. 12 mg was obtained as a white solid.
Melting point: 135-138 ° C
Synthesis Example 10
Production of N- {3-chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -2- (methoxyimino) -3- (methylthio) propanamide (present compound 1-032)
It was produced using the same method as in Synthesis Example 8.
Melting point: 108-112 ° C
Synthesis Example 11
[N- {3-Chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -2- (methoxyimino) -3- (methylthio) propanamide] methyl acetate (present compound 1- 073)
N- {3-chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -2- (methoxyimino) -3- (methylthio) propanamide 500 mg in N, N-dimethylformamide 2 ml solution To this, 88.4 mg of 60 wt% sodium hydride (dispersed in mineral oil) was added at 0 ° C and stirred for 20 minutes. After stirring, 338 mg of bromomethyl acetate was added to the reaction solution, and stirring was continued at room temperature for 2 hours. After completion of the reaction, the reaction solution was poured into ice water and extracted with 50 ml of ethyl acetate. The obtained organic layer was washed with water (50 ml × 2), dehydrated and dried over saturated brine and then anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane-ethyl acetate (gradient 5: 1 to 1: 1) to obtain 302 mg of the desired product as a yellow oil.
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 8.90 (d, J = 2.7 Hz, 1H), 8.61 (dd, J = 4.8, 1.2 Hz, 1H), 8.10-7.90 (m, 2H) , 7.44 (dd, J = 8.4, 4.8 Hz, 1H), 5.80-5.60 (brs, 2H), 3.90-3.60 (brs, 3H), 3.57 ( s, 2H), 2.11 (s, 3H), 2.05-1.85 (brs, 3H)
Synthesis Example 12
N- {3-Chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -2- (methoxyimino) -3- (methylthio) -N- (prop-2-yne-1- Yl) Propanamide (present compound 1-010)
Process 1
Preparation of tert-butyl 3-chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl (prop-2-yn-1-yl) carbamate
60% by weight sodium hydride (dispersed in mineral oil) 1.43 g in a 20 ml N, N-dimethylformamide solution under ice cooling with tert-butyl 3-chloro-1- (pyridin-3-yl) -1H- 9.2 g of pyrazol-4-yl carbamate was added. After completion of the addition, the temperature was raised to room temperature and stirred at the same temperature for 30 minutes. After the completion of stirring, 4.08 g of propargyl bromide was added to the reaction mixture, and stirring was further continued at room temperature for 15 minutes. After completion of the reaction, the reaction mixture was poured into ice water and extracted with 100 ml of ethyl acetate. The obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane-ethyl acetate (gradient 9: 1 to 1: 1) to obtain 9.4 g of the desired product as a light brown amorphous. It was.
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 8.92 (d, J = 2.7 Hz, 1H), 8.57 (d, J = 4.8 Hz, 1H), 8.20-7.80 (m, 2H), 7.41 (dd, J = 8.1, 4.8 Hz, 1H), 4.00-3.00 (m, 2H), 2.29 (t, J = 2.4 Hz, 1H), 1.47 (s, 9H)
Process 2
Preparation of 3-chloro-N- (prop-2-yn-1-yl) -1- (pyridin-3-yl) -1H-pyrazol-4-amine
To a solution of 9.4 g of tert-butyl 3-chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl (prop-2-yn-1-yl) carbamate in 15 ml of 1,4-dioxane, 50 ml of 1,4-dioxane solution of 4M hydrogen chloride was added and stirred overnight at room temperature. After completion of the reaction, the solid precipitated in the reaction solution was taken out by filtration. The obtained solid was suspended in 50 ml of dichloromethane. The suspension was cooled to 0 ° C., a solution of 2.5 g of sodium hydroxide in 10 ml of water was added, and the mixture was stirred at the same temperature for 1 hour. After completion of the reaction, extraction with dichloromethane (30 ml × 3) was performed. The obtained organic layer was dehydrated and dried with saturated brine and then anhydrous sodium sulfate. After evaporating the solvent under reduced pressure, the obtained solid was washed with diisopropyl ether to obtain 5.9 g of the desired product as a yellowish white solid.
Melting point: 131-133 ° C
Process 3
N- {3-Chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -2- (methoxyimino) -3- (methylthio) -N- (prop-2-yne-1- Yl) Propanamide (present compound 1-022)
To a solution of 0.84 g of 2- (methoxyimino) -3- (methylthio) propanoic acid in 10 ml of dichloromethane was added 0.65 g of oxalyl chloride and then 0.1 ml of N, N-dimethylformamide at room temperature. After completion of the addition, the mixture was stirred at the same temperature for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure. The residue obtained was prepared by separately preparing 3-chloro-N- (prop-2-yn-1-yl) -1- (pyridin-3-yl) -1H-pyrazol-4-amine (1.0 g) and pyridine. 0.51 g of dichloromethane in 10 ml solution was added. After the addition was complete, stirring was continued overnight at room temperature. After completion of the reaction, the reaction solution was added to 20 ml of water and extracted with chloroform (20 ml × 2). The obtained organic layer was washed and dried in the order of saturated brine and then anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane-ethyl acetate (9: 1 to 1: 1 gradient) to obtain 1.67 g of the objective product as a yellow oil. Obtained. The obtained target product was a mixture of two geometric isomers, and the isomer ratio was 7: 1.
Isomeric ratio 7
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 8.92 (d, J = 2.7 Hz, 1H), 8.60 (dd, J = 4.8, 1.2 Hz, 1H), 8.09 (s, 1H), 8.02 (Ddd, J = 8.7, 2.7, 1.2 Hz, 1H), 7.44 (dd, J = 8.7, 4.8 Hz, 1H), 4.60-4.40 (m, 2H) ), 3.70 (s, 3H), 3.55 (s, 2H), 2.28 (t, J = 2.4 Hz, 1H), 1, 93 (s, 3H)
Isomer ratio 1
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 8.92 (d, J = 2.7 Hz, 1H), 8.60 (dd, J = 4.8, 1.2 Hz, 1H), 8.09 (s, 1H), 8.02 (Ddd, J = 8.7, 2.7, 1.2 Hz, 1H), 7.44 (dd, J = 8.7, 4.8 Hz, 1H), 4.80-4.60 (m, 2H) ), 4.08 (s, 3H), 3.56 (s, 2H), 2.28 (t, J = 2.4 Hz, 1H), 2.15 (s, 3H)
Synthesis Example 13
N- {3-Chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -2- (methoxyimino) -3- (methylsulfonyl) -N- (prop-2-yne-1) -Il) Production of propanamide (Compound 1-012 of the present invention)
It was produced using the same method as in Synthesis Example 7.
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 8.97 (d, J = 2.7 Hz, 1H), 8.59 (dd, J = 4.8, 1.2 Hz, 1H), 8.16 (s, 1H), 7.98 (Ddd, J = 8.1, 2.7, 1.2 Hz, 1H), 7.41 (dd, J = 8.1, 4.8 Hz, 1H), 4.60-4.40 (m, 4H ), 3.82 (s, 3H), 2.88 (s, 3H), 2.29 (t, J = 2.4 Hz, 1H)
Synthesis Example 14
N- {3-Chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -2- (methoxyimino) -3- (methylsulfonyl) -N- (prop-2-yne-1) -Ill) but-3-enamide (present compound 1-064)
N- {3-Chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -2- (methoxyimino) -3- (methylsulfonyl) -N- (prop-2-yne-1) -Yl) propanamide To a solution of 200 mg of N, N-dimethylformamide in 2.5 ml, 75 mg of N, N, N ′, N′-tetramethyldiaminomethane and 75 mg of acetic anhydride were sequentially added, followed by 2 hours at 60 ° C. . After stirring, stirring was continued overnight at room temperature. After completion of the reaction, the reaction solution was added to water and extracted with 20 ml of ethyl acetate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane-ethyl acetate (4: 1 to 1: 9 gradient) to obtain 120 mg of the desired product as a white solid.
Melting point: 133-134 ° C
Synthesis Example 15
N- {3-Chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -2- (methoxyimino) -2- {1- (methylsulfonyl) cyclopropyl} -N- (prop Preparation of 2-in-1-yl) acetamide (the present compound 1-033)
N- {3-Chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -2- (methoxyimino) -3- (methylsulfonyl) -N- (prop-2-yne-1) -Yl) To 150 mg of propanamide in 4 ml of acetone, 150 mg of potassium carbonate, 110 mg of 1,2-dibromoethane and 65 mg of 18-crown 6-ether were sequentially added and stirred at 65 ° C. for 7 hours. After completion of the reaction, the reaction solution was added to water and extracted with ethyl acetate (4 ml × 3), and then the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane-ethyl acetate (4: 1 to 1: 3 gradient) to obtain 65 mg of the objective product as a colorless oil. The obtained target product was a mixture of two geometric isomers, and the isomer ratio was 5: 1.
Isomer ratio 5
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 8.97 (d, J = 2.4 Hz, 1H), 8.60 (dd, J = 4.8, 1.2 Hz, 1H), 8.24 (s, 1H), 8.00 (Ddd, J = 8.4, 2.4, 1.2 Hz, 1H), 7.43 (dd, J = 8.4, 4.8 Hz, 1H), 4.60-4.40 (m, 2H) ), 3.83 (s, 3H), 2.71 (s, 3H), 2.29 (t, J = 2.4 Hz, 1H), 1.75-1.60 (m, 4H)
Isomer ratio 1
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 9.00 (d, J = 2.1 Hz, 1H), 8.60 (dd, J = 4.8, 1.2 Hz, 1H), 8.25 (s, 1H), 8.06 −8.00 (m, 1H), 7.43 (dd, J = 8.4, 4.8 Hz, 1H), 4.60-4.40 (m, 2H), 3.83 (s, 3H) , 3.11 (s, 3H), 2.26 (t, J = 2.1 Hz, 1H), 1.75-1.60 (m, 4H)
Synthesis Example 16
N- {3-Chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -N- (1-methoxyethyl) -2- (methoxyimino) -3- (methylthio) butanamide (present) Production of Inventive Compound 1-113)
N- {3-Chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -2- (methoxyimino) -3- (methylthio) butanamide in a 5 ml dichloromethane solution at 0 ° C. Dimethylacetal 256 mg, N, N-diisopropylethylamine 366 mg, and trifluoromethanesulfonic acid trimethylsilane 631 mg were sequentially added. After the addition was complete, the mixture was stirred overnight at room temperature. After completion of the reaction, 50 ml of dichloromethane was added to the reaction solution, washed with a saturated aqueous sodium hydrogen carbonate solution, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, the obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane-ethyl acetate (9: 1 to 3: 2 gradient), The desired product (85.7 mg) was obtained as a colorless oil. The obtained target product was a mixture of two kinds of geometric isomers, and the isomer ratio was 83:10.
Isomeric ratio 83
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 8.94 (d, J = 2.7 Hz, 1H), 8.65-8.55 (m, 1H), 8.10-8.00 (m, 1H), 7.91 (s) , 1H), 7.50-7.40 (m, 1H), 6.15-5.95 (m, 1H), 4.10-3.90 (m, 1H), 3.75 (s, 3H) ), 3.53 (s, 3H), 1.86 (brs, 3H), 1.55-1.20 (m, 6H)
Isomeric ratio 10
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 9.00-8.90 (m, 1H), 8.65-8.55 (m, 1H), 8.10-8.00 (m, 1H), 7.89 (s, 1H) ), 7.50-7.40 (m, 1H), 5.55-5.35 (m, 1H), 4.10-3.90 (m, 1H), 3.55 (s, 3H), 3.53 (s, 3H), 2.08 (brs, 3H), 1.55-1.20 (m, 6H)
Synthesis Example 17
2- [2-[{3-Chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl} amino] -2-oxoethylidene] -N- (2,6-dichlorophenyl) hydrazinecarboxamide ( Production of the present compound 1-227)
Process 1
Preparation of 2- [2-{(2,6-dichlorophenyl) carbamoyl} hydrazono] acetic acid
To a solution of 3 g of N- (2,6-dichlorophenyl) hydrazinecarboxamide in 30 ml of ethanol was added 2.5 g of an approximately 9 mol / L glyoxylic acid aqueous solution. After completion of the addition, the reaction solution was stirred overnight at room temperature. After completion of the reaction, the solvent was distilled off from the reaction solution under reduced pressure, and the resulting solid was added to 30 ml of 2N aqueous sodium hydroxide solution. After completion of the addition, insoluble matter precipitated in the solution was removed by filtration. The obtained filtrate was adjusted to pH 3 with concentrated hydrochloric acid, and the precipitated solid was removed by filtration. The obtained solid was washed with water and dried under reduced pressure to obtain 2.5 g of the desired product as a white solid.
Melting point: 238-242 ° C
Process 2
2- [2-[{3-Chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl} amino] -2-oxoethylidene] -N- (2,6-dichlorophenyl) hydrazinecarboxamide Manufacturing
2- [2-{(2,6-dichlorophenyl) carbamoyl} hydrazono] acetic acid (235 mg) in dichloromethane (4 ml) was added 3-chloro-1- (pyridin-3-yl) -1H-pyrazol-4-amine (150 mg), 1- 223 mg of ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was added sequentially. After completion of the addition, the reaction solution was stirred at room temperature for 2 hours. After completion of the reaction, 4 ml of water was added to the reaction solution. After completion of the addition, the solid precipitated in the solution was taken out by filtration. The obtained solid was washed with water and then with isopropyl ether, and then dried under reduced pressure to obtain 280 mg of the desired product as a white solid.
Melting point: 211-214 ° C
Synthesis Example 18
Preparation of 2- (hydroxyimino) -N- {3-methyl-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -3- (methylthio) butanamide
To a solution of 280 mg 2- (hydroxyimino) -3- (methylthio) butanoic acid and 300 mg 3-methyl-1- (pyridin-3-yl) -1H-pyrazol-4-amine in 6 ml dichloromethane was added 1-ethyl-3- 396 mg of (3-dimethylaminopropyl) carbodiimide hydrochloride was added and stirred at room temperature for 1 hour. After completion of the reaction, the reaction solution was washed with 10 ml of water, and then the solvent was distilled off under reduced pressure. After the solvent was distilled off, the resulting solid was washed with diisopropyl ether to obtain 160 mg of the desired product as a white solid.
Melting point: 207-209 ° C
[Reference example]
Reference example 1
Production of 3-chloro-1- (pyridin-3-yl) -1H-pyrazol-4-amine (Part 1)
To a solution of 10.7 g of 3-chloro-1H-pyrazol-4-amine in 70 ml of toluene, 12.7 g of 3-bromopyridine, 2.65 g of copper iodide (monovalent), 28.9 g of potassium carbonate, trans-N, N′-dimethylcyclohexane-1,2-diamine 3.96 g and dimethyl sulfoxide 20 ml were sequentially added. After completion of the addition, the inside of the reaction vessel was replaced with nitrogen gas and then stirred at 100 ° C. for 2 hours. After completion of the reaction, the solid precipitated in the reaction mixture was filtered off. To the obtained filtrate, 100 ml of ethyl acetate was added, washed with 50 ml of a 7% by weight aqueous ammonia solution and then with saturated brine, and then dehydrated and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure. The obtained solid was washed with diisopropyl ether to obtain 8.52 g of the desired product as a brown solid.
Melting point: 139-143 ° C
Reference example 2
Production of 3-chloro-1- (pyridin-3-yl) -1H-pyrazol-4-amine (Part 2)
Process 1
Preparation of ethyl 3-chloro-1H-pyrazole-4-carboxylate
30 ml of concentrated hydrochloric acid was added to 9.71 g of ethyl 1-tert-butyl-5-chloro-1H-pyrazole-4-carboxylate under ice cooling. After the addition was complete, the mixture was stirred overnight at room temperature. After completion of the stirring, 10 ml of concentrated hydrochloric acid was added to the reaction mixture, and stirring was continued for a whole day and night. After completion of the reaction, the reaction mixture was cooled to 0 ° C., neutralized with an aqueous sodium hydroxide solution, and extracted with 100 ml of ethyl acetate. The obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained solid was washed with n-hexane to obtain 6.28 g of the desired product as a white solid.
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 11.2 (brs, 1H), 8.10 (s, 1H), 4.33 (q, J = 7.2 Hz, 2H), 1.36 (t, J = 7.2 Hz, 3H) )
Process 2
Preparation of ethyl 3-chloro-1- (pyridin-3-yl) -1H-pyrazole-4-carboxylate
A solution of 10.2 g of ethyl 3-chloro-1H-pyrazole-4-carboxylate in 150 ml of N, N-dimethylformamide was added to 15.6 g of 3-iodopyridine, 2.23 g of copper iodide (monovalent) and cesium carbonate 33. 0 g was added sequentially. After completion of the addition, the inside of the reaction vessel was replaced with nitrogen gas, followed by stirring at 130 ° C. for 5 hours. After completion of the reaction, the reaction mixture was allowed to cool to room temperature and 100 ml of 1N aqueous sodium hydroxide solution was added. Impurities in the reaction mixture were removed by Celite filtration under reduced pressure, and the obtained filtrate was extracted with 100 ml of ethyl acetate. The obtained organic layer was washed and dried in the order of saturated brine and then anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane-ethyl acetate (1: 1 gradient) to obtain 7.56 g of the desired product as a white solid.
Melting point: 90-93 ° C.

Process 3
Preparation of 3-chloro-1- (pyridin-3-yl) -1H-pyrazole-4-carboxylic acid 16.75 g of ethyl 3-chloro-1- (pyridin-3-yl) -1H-pyrazole-4-carboxylate 5.6 g of potassium hydroxide and 130 ml of water were sequentially added to a 130 ml solution of ethanol. After the addition was complete, the mixture was stirred overnight at room temperature. After completion of the reaction, 2N hydrochloric acid aqueous solution was added to adjust the pH of the reaction mixture to 4. Then, the precipitated solid was removed by filtration, and the removed solid was washed with water. The obtained solid was added to 200 ml of toluene and dehydrated using a Dean-Stark tube while the toluene was refluxed. After completion of dehydration, the solid in toluene was removed by filtration to obtain 14.5 g of the desired product as a light pink solid.
Melting point: 275-282 ° C.

Process 4
Production of 3- (3-chloro-4-nitro-1H-pyrazol-1-yl) pyridine 1.72 ml of acetic anhydride was added dropwise at a temperature of 40 ° C. or lower to a solution of concentrated hydrochloric acid 9 ml and fuming nitric acid 3.1 ml. After completion of the dropwise addition, the reaction mixture was stirred at room temperature for 30 minutes. After stirring, the reaction mixture was heated to 60 ° C. After completion of the heating, 5 g of 3-chloro-1- (pyridin-3-yl) -1H-pyrazole-4-carboxylic acid was added to the reaction mixture in 5 portions while maintaining 60 ° C. After completion of the addition, stirring was continued at 65 ° C. for 2 hours. After completion of the reaction, the reaction mixture was poured into ice water and neutralized with 1N aqueous sodium hydroxide solution. The precipitated solid was filtered, washed with water, and dried to obtain 4.2 g of the desired product as a pale yellow solid.
Melting point: 139-140 ° C
Process 5
Preparation of 3-chloro-1- (pyridin-3-yl) -1H-pyrazol-4-amine 3- (3-chloro-4-nitro-1H-pyrazol-1-yl) pyridine 4 g of ethyl acetate 20 ml, acetic acid 10 ml of water and 10 ml of water were heated to 65 ° C., and 2.5 g of reduced iron was added little by little. After completion of the addition, the mixture was stirred at 70 ° C. for 2 hours. After completion of the reaction, the reaction solution was allowed to cool to room temperature, 50 ml of water was added, and the pH of the reaction solution was adjusted to 10 with sodium bicarbonate. The insoluble matter in the reaction solution was removed by filtration, and the organic layer of the filtrate was taken out by liquid separation. The obtained organic layer was dehydrated and dried in the order of saturated brine and then anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained solid was washed with diisopropyl ether to obtain 2.6 g of the desired product as a light purple solid.
Melting point: 142-144 ° C
The following intermediates were synthesized by the same synthesis method as in Reference Example 2.

3- (3-Methyl-4-nitro-1H-pyrazol-1-yl) pyridine
Melting point: 121-122 ° C
Reference example 3
Preparation of ethyl 3-chloro-1H-pyrazole-4-carboxylate
1 g of ethyl 3-amino-1H-pyrazole-4-carboxylate was added to a solution of 2.2 ml of concentrated hydrochloric acid, 2.2 ml of acetic acid and 1.3 ml of phosphoric acid, and cooled to -5 ° C. After completion of cooling, a solution of 0.49 g of sodium nitrite in 1 ml of water was added dropwise to the reaction mixture while maintaining the temperature at −5 ° C. to prepare a diazonium salt solution. Separately, 6.4 ml of concentrated hydrochloric acid was cooled to 0 ° C., and a solution of 0.73 g of sodium bisulfite in 1.5 ml of water was added dropwise while maintaining 0 ° C. After the completion of dropping, 0.16 g of copper sulfate pentahydrate was added. After completion of the addition, the previously prepared diazonium salt solution and a solution of 0.73 g of sodium bisulfite in 1.5 ml of water were added dropwise to the reaction mixture while maintaining the temperature at 0 ° C. After completion of the dropwise addition, the mixture was stirred for 10 minutes, poured into ice water, and neutralized with an aqueous potassium hydroxide solution. Extraction was performed with chloroform (20 ml × 3), and the obtained organic layer was dehydrated and dried over saturated brine and then anhydrous sodium sulfate. The obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane-ethyl acetate (gradient 5: 1 to 1: 2) to obtain 426 mg of the desired product as a white solid.
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 11.2 (brs, 1H), 8.10 (s, 1H), 4.33 (q, J = 7.2 Hz, 2H), 1.36 (t, J = 7.2 Hz, 3H) )
Reference example 4
Production of 2- (methoxyimino) -3- (methylthio) propanoic acid
Process 1
Preparation of ethyl 2- (methoxyimino) -3- (methylthio) propanoate
To a solution of 2.0 g of ethyl 3-bromo-2- (methoxyimino) propanoate in 30 ml of N, N-dimethylformamide was added 750 mg of sodium methyl mercaptan. After completion of the addition, the mixture was stirred at room temperature for 2 hours. After completion of the stirring, the reaction mixture was heated to 80 ° C. and then stirred at the same temperature for 1 hour. After completion of the reaction, 30 ml of water was added to the reaction mixture and extracted with 50 ml of ethyl acetate. The obtained organic layer was washed with a saturated aqueous solution of sodium hydrogen carbonate, washed with saturated brine and then dried over anhydrous sodium sulfate in that order. The solvent was distilled off under reduced pressure to obtain 2 g of the desired product as a pale yellow oil.
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 4.34 (q, J = 7.2 Hz, 2H), 4.04 (s, 3H), 3.55 (s, 2H), 2.10 (s, 3H), 1.35 ( t, J = 7.2 Hz, 3H)
Process 2
Production of 2- (methoxyimino) -3- (methylthio) propanoic acid
Ethyl 2- (methoxyimino) -3- (methylthio) propanoate To a mixed solution of 1.84 g of water and 10 ml of ethanol was added 430 mg of sodium hydroxide. After completion of the addition, the mixture was stirred at room temperature for 2 days. After completion of the reaction, 1N aqueous hydrochloric acid solution was added to the reaction solution to adjust the pH of the reaction solution to 2, and the mixture was extracted with ethyl acetate (20 ml × 2). The obtained organic layer was washed and dried in the order of saturated brine and then anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained solid was washed with 6 ml of a mixed solution of hexane: isopropyl ether (5: 1) to obtain 0.4 g of the objective product as a yellowish white solid.
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 4.08 (s, 3H), 3.53 (s, 2H), 2.14 (s, 3H)
Reference Example 5
Production of 2- (methoxyimino) -3- (methylthio) butanoic acid
Process 1
Preparation of ethyl 2- (methoxyimino) -3- (tosyloxy) butanoate (Compound D-001)
To a solution of 1.63 g of ethyl 3-hydroxy-2- (methoxyimino) butanoate synthesized in accordance with the method described in German Patent Application No. 3220524 in 10 ml of dichloromethane, 2.36 g of triethylamine and p-toluenesulfonyl chloride. 14 g and 4-dimethylaminopyridine 0.34 g were added sequentially. After the addition was complete, the reaction mixture was stirred overnight at room temperature. After completion of the reaction, 20 ml of saturated aqueous sodium hydrogen carbonate solution was added to the reaction solution, and extracted with 30 ml of ethyl acetate. The obtained organic layer was washed with water, then washed and dried with saturated brine and then anhydrous sodium sulfate in this order, and the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane-ethyl acetate (5: 1) to obtain 0.8 g of the objective product as a yellow oil.
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 7.78 (d, J = 8.1 Hz, 2H), 7.32 (d, J = 8.1 Hz, 2H), 5.31 (q, J = 6.9 Hz, 1H), 4 .28-4.16 (m, 2H), 3.82 (s, 3H), 2.44 (s, 3H), 1.53 (d, J = 6.9 Hz, 3H), 1.27 (t , J = 7.2Hz, 3H)
Process 2
Preparation of ethyl 2- (methoxyimino) -3- (methylthio) butanoate (Compound E-001)
To a solution of 0.8 g of ethyl 2- (methoxyimino) -3- (tosyloxy) butanoate in 5 ml of N, N-dimethylformamide was added 0.2 g of sodium methyl mercaptan at 0 ° C. After completion of the addition, the mixture was stirred at the same temperature for 30 minutes. After completion of the reaction, 10 ml of water was added to the reaction solution and extracted with 10 ml of ethyl acetate. The obtained organic layer was washed and dried in the order of saturated brine and then anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 0.45 g of the desired product as a yellow oil.
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 4.32 (q, J = 7.2 Hz, 2H), 3.87 (s, 3H), 3.60 (q, J = 7.2 Hz, 1H), 2.05 (s, 3H) ), 1.46 (d, J = 7.2 Hz, 3H), 1.33 (t, J = 7.2 Hz, 3H)
Process 3
Production of 2- (methoxyimino) -3- (methylthio) butanoic acid (Compound F-001)
To a solution of ethyl 2- (methoxyimino) -3- (methylthio) butanoate 0.45 g in ethanol 5 ml was added 1N sodium hydroxide aqueous solution 3.3 ml. . After completion of the addition, the mixture was stirred at room temperature for 2 hours. After completion of the reaction, ethanol was distilled off from the reaction solution under reduced pressure. The resulting residue was washed with ethyl acetate. After the completion of washing, the pH was adjusted to 3 with 1N aqueous hydrochloric acid solution, followed by extraction with ethyl acetate (5 ml × 2). The obtained organic layer was washed and dried in the order of saturated brine and then anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to obtain 0.4 g of the objective product as a yellow oil.
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 4.06 (s, 3H), 3.88-3.77 (m, 1H), 2.06 (s, 3H), 1.49 (d, J = 6.9 Hz, 3H) ( CO ₂ The proton peak of H was not observed. )
The following intermediates were synthesized by the same synthesis method as in Reference Example 5.
A-002; methyl 2- (hydroxyimino) -3-oxopentanoate
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 9.51 (brs, 1H), 3.91 (s, 3H), 2.81 (q, J = 7.5 Hz, 2H), 1.13 (t, J = 7.5 Hz, 3H) )
A-003; methyl 2- (hydroxyimino) -4-methyl-3-oxopentanoate
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 9.20 (brs, 1H), 3.91 (s, 3H), 3.44-3.30 (m, 1H), 1.22-1.08 (m, 6H)
B-002; Methyl 2- (methoxyimino) -3-oxopentanoate
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 4.09 (s, 3H), 3.87 (s, 3H), 2.81 (q, J = 7.5 Hz, 2H), 1.13 (t, J = 7.5 Hz, 3H) )
B-003; methyl 2- (methoxyimino) -4-methyl-3-oxopentanoate
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 4.09 (s, 3H), 3.87 (s, 3H), 3.43 (sep, J = 7.2 Hz, 1H), 1.16 (d, J = 7.2 Hz, 6H) )
C-002; methyl 3-hydroxy-2- (methoxyimino) pentanoate
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 4.42-4.32 (m, 1H), 3.91 (s, 3H), 3.86 (s, 3H), 2.44-2.32 (m, 1H), 1. 87-1.52 (m, 2H), 0.99 (t, J = 7.5Hz, 3H)
C-003; methyl 3-hydroxy-2- (methoxyimino) -4-methylpentanoate
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 4.17 (dd, J = 5.7, 5.4 Hz, 1H), 3.92 (s, 3H), 3.85 (s, 3H), 2.45 (d, J = 5 .7 Hz, 1H), 1.90 (ttd, J = 6.9, 6.9, 5.4 Hz, 1H), 1.01 (d, J = 6.9 Hz, 3H), 0.97 (d, J = 6.9Hz, 3H)
D-002; methyl 2- (methoxyimino) -3- (tosyloxy) pentanoate
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 7.80 (d, J = 8.7 Hz, 2H), 7.33 (d, J = 8.7 Hz, 2H), 5.02 (t, J = 7.2 Hz, 1H), 3 .80 (s, 3H), 3.76 (s, 3H), 2.45 (s, 3H), 2.00-1.88 (m, 2H), 0.92 (t, J = 7.5 Hz) , 3H)
D-003; methyl 2- (methoxyimino) -4-methyl-3- (tosyloxy) pentanoate
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 7.79 (d, J = 7.8 Hz, 2H), 7.32 (d, J = 7.8 Hz, 2H), 4.71 (d, J = 9.6 Hz, 1H), 3 .76 (s, 3H), 3.75 (s, 3H), 2.44 (s, 3H), 2.20-2.06 (m, 1H), 1.00 (d, J = 6.9 Hz) , 3H), 0.92 (d, J = 6.6 Hz, 3H)
E-002; methyl 2- (methoxyimino) -3- (methylthio) pentanoate
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 3.89 (s, 3H), 3.84 (s, 3H), 3.33 (t, J = 7.5 Hz, 1H), 2.04 (s, 3H), 1.93- 1.60 (m, 2H), 1.05 (t, J = 7.5Hz, 3H)
E-003; methyl 2- (methoxyimino) -4-methyl-3- (methylthio) pentanoate
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 3.89 (s, 3H), 3.84 (s, 3H), 3.08 (d, J = 10.5 Hz, 1H), 2.08-1.92 (m, 1H), 2.06 (s, 3H), 1.15-1.04 (m, 6H)
F-002; 2- (methoxyimino) -3- (methylthio) pentanoic acid
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 4.03 (s, 3H), 3.53 (t, J = 7.8 Hz, 1H), 2.04 (s, 3H), 1.96-1.70 (m, 2H), 1.04 (t, J = 7.2 Hz, 3H) (CO ₂ The proton peak of H was not observed. )
E-006; methyl 3-methoxy-2- (methoxyimino) pentanoate
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 3.91 (s, 3H), 3.84 (s, 3H), 3.75 (t, J = 7.2 Hz, 1H), 3.37 (s, 3H), 1.88- 1.62 (m, 2H), 0.97 (t, J = 7.5 Hz, 3H)
E-008; methyl 2- (methoxyimino) -3-[{5- (trifluoromethyl) pyridin-2-yl} thio] pentanoate (mixture of two isomers, isomer ratio 7: 3)
Isomeric ratio 7
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 8.67-8.62 (m, 1H), 7.68 (dd, J = 8.4, 2.4 Hz, 1H), 7.31-7.19 (m, 1H), 4 .86 (t, J = 7.5 Hz, 1H), 3.90 (s, 3H), 3.78 (s, 3H), 2.14-1.80 (m, 2H), 1.10 (t , J = 7.2Hz, 3H)
Isomer ratio 3
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 8.67-8.62 (m, 1H), 7.68 (dd, J = 8.4, 2.4 Hz, 1H), 7.31-7.19 (m, 1H), 5 .53 (t, J = 8.1 Hz, 1H), 4.10 (s, 3H), 3.88 (s, 3H), 2.14-1.80 (m, 2H), 1.01 (t , J = 7.5Hz, 3H)
E-009; methyl 2- (methoxyimino) -3-{(2,2,2-trifluoroethyl) thio} pentanoate
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 3.91 (s, 3H), 3.85 (s, 3H), 3.65-3.55 (m, 1H), 3.25-2.93 (m, 2H), 1. 90-1.60 (m, 2H), 1.07 (t, J = 7.2 Hz, 3H)
E-010; ethyl 2- (methoxyimino) -3- (methylsulfonyl) -5-hexenoate
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 5.74-5.58 (m, 1H), 5.20-5.07 (m, 2H), 4.92 (dd, J = 10.8, 5.4 Hz, 1H), 4 .34 (q, J = 7.2 Hz, 2H), 4.14 (s, 3H), 3.16-2.87 (m, 2H), 2.99 (s, 3H), 1.36 (t , J = 7.2Hz, 3H)
E-011; ethyl 2- (methoxyimino) -3- (methylsulfonyl) -5-hexinoate
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 5.04 (dd, J = 9.6, 6.6 Hz, 1H), 4.46-4.32 (m, 2H), 4.17 (s, 3H), 3.33-3 .07 (m, 2H), 3.00 (s, 3H), 2.08 (t, J = 2.4 Hz, 1H), 1.44-1.30 (m, 3H)
E-012; methyl 3- (allylthio) -2- (methoxyimino) pentanoate (mixture of two isomers, isomer ratio 7: 3)
Isomeric ratio 7
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 5.85-5.66 (m, 1H), 5.18-5.02 (m, 2H), 3.87 (s, 3H), 3.83 (s, 3H), 3. 43-3.02 (m, 2H), 2.65-2.45 (m, 1H), 2.05-1.60 (m, 2H), 1.30-0.87 (m, 3H)
Isomer ratio 3
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 5.85-5.66 (m, 1H), 5.18-5.02 (m, 2H), 4.00 (s, 3H), 3.83 (s, 3H), 3. 43-3.02 (m, 2H), 2.65-2.45 (m, 1H), 2.05-1.60 (m, 2H), 1.30-0.87 (m, 3H)
F-002; 2- (methoxyimino) -3- (methylthio) pentanoic acid
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 4.03 (s, 3H), 3.53 (t, J = 7.8 Hz, 1H), 2.04 (s, 3H), 1.96-1.70 (m, 2H), 1.04 (t, J = 7.2 Hz, 3H) (CO ₂ The proton peak of H was not observed. )
F-003; 2- (methoxyimino) -4-methyl-3- (methylthio) pentanoic acid (mixture of two isomers, isomer ratio 55:45)
Isomeric ratio 55
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 4.15 (d, J = 6.9 Hz, 1H), 4.10 (s, 3H), 2.20-2.01 (m, 1H), 2.05 (s, 3H), 1.01 (d, J = 6.9 Hz, 3H), 0.95 (d, J = 6.9 Hz, 3H) (CO ₂ The proton peak of H was not observed. )
Isomer ratio 45
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 4.03 (s, 3H), 3.23 (d, J = 10.5 Hz, 1H), 2.20-2.01 (m, 1H), 2.05 (s, 3H), 1.15 (d, J = 6.6 Hz, 3H), 1.02 (d, J = 6.9 Hz, 3H) (CO ₂ The proton peak of H was not observed. )
F-006; 3-methoxy-2- (methoxyimino) pentanoic acid
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 4.02 (s, 3H), 3.89 (t, J = 7.2 Hz, 1H), 3.40 (s, 3H), 1.92-1.70 (m, 2H), 0.94 (t, J = 7.2 Hz, 3H) (CO ₂ The proton peak of H was not observed. )
F-008; 2- (methoxyimino) -3-[{5- (trifluoromethyl) pyridin-2-yl} thio] pentanoic acid
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 8.70-8.60 (m, 1H), 7.75-7.63 (m, 1H), 7.30-7.20 (m, 1H), 5.44 (t, J = 7.8 Hz, 1 H), 4.12 (s, 3 H), 2.20-1.95 (m, 2 H), 1.00 (t, J = 7.5 Hz, 3 H)
F-009; 2- (methoxyimino) -3-{(2,2,2-trifluoroethyl) thio} pentanoic acid
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 4.07 (s, 3H), 3.78-3.70 (m, 1H), 3.30-2.97 (m, 2H), 2.03-1.70 (m, 2H) ), 1.05 (t, J = 7.2 Hz, 3H)
F-010; 2- (methoxyimino) -3- (methylsulfonyl) -5-hexenoic acid (mixture of two isomers, isomer ratio 3: 2)
Isomer ratio 3
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 5.82-5.56 (m, 1H), 5.25-5.10 (m, 2H), 4.85 (dd, J = 11.1, 4.8 Hz, 1H), 4 .18 (s, 3H), 3.29-2.78 (m, 2H), 3.04 (s, 3H)
Isomer ratio 2
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 5.82-5.56 (m, 1H), 5.25-5.10 (m, 2H), 4.45 (dd, J = 10.8, 4.8 Hz, 1H), 4 .18 (s, 3H), 3.29-2.78 (m, 2H), 2.95 (s, 3H)
F-010; 2- (methoxyimino) -3- (methylsulfonyl) -5-hexynoic acid (mixture of two isomers, isomer ratio 3: 2)
Isomer ratio 3
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 4.98 (dd, J = 10.2, 6.6 Hz, 1H), 4.21 (s, 3H), 3.38-3.25 (m, 1H), 3.20-2 .96 (m, 1H), 3.04 (s, 3H), 2.14 to 2.06 (m, 1H)
Isomer ratio 2
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) [delta] 4.73-4.67 (m, 1H), 4.23 (s, 3H), 3.65-3.48 (m, 1H), 3.20-2.96 (m, 1H) ), 3.06 (s, 3H), 2.18 (t, J = 2.4 Hz, 1H)
F-011; 3- (allylthio) -2- (methoxyimino) pentanoic acid (mixture of two isomers, isomer ratio 7: 3)
Isomeric ratio 7
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 5.90-5.70 (m, 1H), 5.22-5.06 (m, 2H), 4.02 (s, 3H), 3.60-3.04 (m, 2H) ), 2.70-2.48 (m, 1H), 2.10-1.72 (m, 2H), 1.08-0.85 (m, 3H)
Isomer ratio 35.90-5.70 (m, 1H), 5.22-5.06 (m, 2H), 4.05 (s, 3H), 3.60-3.04 (m, 2H) , 2.70-2.48 (m, 1H), 2.10-1.72 (m, 2H), 1.08-0.85 (m, 3H)
Reference Example 6
Production of 3- (ethylthio) -2- (methoxyimino) butanoic acid
Process 1
Production of 3- (ethylthio) -2-oxobutanoic acid
6.8 g of N-bromosuccinimide and 241 mg of 2,2′-azobis (isobutyronitrile) were sequentially added to a solution of 3 g of 2-oxobutyric acid in 20 ml of 1,2-dichloroethane, and the inside of the reaction vessel was replaced with nitrogen gas. Thereafter, the mixture was stirred at 80 ° C. for 1 hour. After completion of the reaction, the reaction solution was cooled to 0 ° C., 10 ml of acetone, 5.2 g of potassium carbonate, and 2.5 g of sodium ethyl mercaptan were sequentially added, followed by stirring at room temperature for 1 hour. After completion of the reaction, 30 ml of hexane and 30 ml of water were added to the reaction solution, and the aqueous layer was taken out by a liquid separation operation. To the obtained aqueous layer, 10 ml of concentrated hydrochloric acid was added, followed by extraction with 50 ml of ethyl acetate. The obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain 5 g of the desired product as a yellow oil.
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 4.25-4.10 (m, 1H), 2.60-2.30 (m, 2H), 1.50 (d, J = 7.2 Hz, 3H), 1.22 (t , J = 7.5Hz, 3H) (CO ₂ The proton peak of H was not observed. )
Process 2
Production of 3- (ethylthio) -2- (methoxyimino) butanoic acid (Compound F-004)
To a solution of 1 g of 3- (ethylthio) -2-oxobutanoic acid in 10 ml of methanol and 5 ml of water, 1 g of O-methylhydroxylamine hydrochloride was added and stirred at room temperature for 15 hours. After completion of the reaction, 2 g of sodium hydroxide, 10 ml of water and 10 ml of hexane were sequentially added to the reaction solution, and the aqueous layer was taken out by a liquid separation operation. Concentrated hydrochloric acid was added to the obtained aqueous layer to adjust the pH of the aqueous layer to 2, and then 3 g of sodium chloride was added and extracted with 30 ml of ethyl acetate. The obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 250 mg of the desired product as a yellow oil. The obtained target product was a mixture of two geometric isomers, and the isomer ratio was 2: 1.
Isomer ratio 2
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 4.06 (s, 3H), 4.20-4.05 (m, 1H), 2.65-2.45 (m, 2H), 1.56 (d, J = 7.5 Hz) , 3H), 1.24 (t, J = 7.5 Hz, 3H) (CO ₂ The proton peak of H was not observed. )
Isomer ratio 1
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 4.01 (s, 3H), 3.90-3.80 (m, 1H), 2.65-2.45 (m, 2H), 1.51 (d, J = 7.5 Hz , 3H), 1.25 (t, J = 7.5 Hz, 3H) (CO ₂ The proton peak of H was not observed. )
The following intermediates were synthesized by the same synthesis method as in Reference Example 6.
F-005; 2- (ethoxyimino) -3- (ethylthio) butanoic acid (mixture of two isomers, isomer ratio 1: 1)
Isomer ratio 1
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 4.40-4.25 (m, 2H), 3.90 (q, J = 7.5 Hz, 1H), 2.65-2.45 (m, 2H), 1.57 (d , J = 7.5 Hz, 3H), 1.34 (t, J = 7.5 Hz, 3H), 1.24 (t, J = 7.5 Hz, 3H) (CO ₂ The proton peak of H was not observed. )
Isomer ratio 1
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 4.45-4.35 (m, 1H), 4.40-4.25 (m, 2H), 2.65-2.45 (m, 2H), 1.52 (d, J = 7.5 Hz, 3 H), 1.34 (t, J = 7.5 Hz, 3 H), 1.24 (t, J = 7.5 Hz, 3 H) (CO ₂ The proton peak of H was not observed. )
F-001; 2- (methoxyimino) -3- (methylthio) butanoic acid (mixture of two isomers, isomer ratio 1: 1)
Isomer ratio 1
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 4.28 (q, J = 7.2 Hz, 1H), 4.06 (s, 3H), 2.10 (s, 3H), 1.56 (d, J = 7.5 Hz, 3H) ) (CO ₂ The proton peak of H was not observed. )
Isomer ratio 1
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 3.98 (s, 3H), 3.75 (q, J = 7.2 Hz, 1H), 2.09 (s, 3H), 1.49 (d, J = 7.5 Hz, 3H ) (CO ₂ The proton peak of H was not observed. )
Reference Example 7
Preparation of 2- (methoxyimino) -N- (3-methyl-1H-pyrazol-4-yl) -3- (methylthio) butanamide
Process 1
Preparation of 1- (tert-butyl) -5-methyl-1H-pyrazole-4-carboxylic acid
Journal of Heterocyclic Chemistry 1987, Vol. 24, p. 693, synthesized in accordance with the method described in Ethyl 1- (tert-butyl) -5-methyl-1H-pyrazole-4-carboxylate 16.7 g of ethanol 50 ml and water To 50 ml of the solution, 3.5 g of sodium hydroxide was added, stirred at room temperature overnight, and then stirred at 60 ° C. for 3 hours. After completion of the reaction, the solvent of the reaction solution was distilled off under reduced pressure, 50 ml of water was added to the residue, and the mixture was washed with 50 ml of ethyl acetate. Concentrated hydrochloric acid was added to the obtained aqueous layer to adjust the pH to 1, and the solid deposited in the aqueous layer was taken out by filtration and washed with water. The obtained solid was dried under reduced pressure to obtain 9.0 g of the objective product as a white solid.
Melting point: 108-109 ° C
Process 2
Preparation of 1- (tert-butyl) -5-methyl-1H-pyrazole-4-carboxamide
To a solution of 1 g of 1- (tert-butyl) -5-methyl-1H-pyrazole-4-carboxylic acid in 10 ml of dichloromethane was added 0.84 g of oxalyl chloride and then 0.1 ml of N, N-dimethylformamide at room temperature. . After completion of the addition, the mixture was stirred at the same temperature for 30 minutes. After completion of the reaction, the solvent was distilled off under reduced pressure. Tetrahydrofuran (15 ml) was added to the obtained residue, and added at 0 ° C. to 28% ammonia aqueous solution (15 ml). After completion of the addition, stirring was continued at 0 ° C. for 30 minutes. After completion of the reaction, the reaction solution was extracted with 30 ml of ethyl acetate, and then the solvent was distilled off under reduced pressure to obtain 0.48 g of the desired product as a white solid.
Melting point: 137-140 ° C
Process 3
Preparation of 1- (tert-butyl) -5-methyl-1H-pyrazol-4-amine
To a solution of 0.64 g of sodium hydroxide in 0.5 ml of water, 5.2 g of an 8% aqueous sodium hypochlorite solution and 2 ml of water were added and cooled to 0 ° C. To the reaction solution, 0.48 g of 1- (tert-butyl) -5-methyl-1H-pyrazole-4-carboxamide was added and stirred at 70 ° C. for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature and extracted with 10 ml of ethyl acetate. The obtained organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and 0.23 g of the desired product was obtained as a brown oil.
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 7.11 (s, 1H), 2.63 (brs, 2H), 2.33 (s, 3H), 1.58 (s, 9H)
Process 4
Preparation of N- {1- (tert-butyl) -5-methyl-1H-pyrazol-4-yl} -2- (methoxyimino) -3- (methylthio) butanamide
To a solution of 0.4 g of 2- (methoxyimino) -3- (methylthio) butanoic acid in 5 ml of dichloromethane was added 0.38 g of oxalyl chloride and then 0.1 ml of N, N-dimethylformamide at room temperature. After completion of the addition, the mixture was stirred at the same temperature for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure. The obtained residue was added at 0 ° C. to a separately prepared solution of 0.23 g of 1- (tert-butyl) -5-methyl-1H-pyrazol-4-amine and 0.36 g of pyridine in 5 ml of dichloromethane. After completion of the addition, stirring was continued for 1 hour at 0 ° C. After completion of the reaction, the reaction solution was washed with 10 ml of water. The obtained organic layer was washed and dried in the order of saturated brine and then anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane-ethyl acetate (1: 1) to obtain 0.34 g of the desired product as a brown oil.
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 7.97 (brs, 1H), 7.61 (s, 1H), 4.34 (q, J = 7.2 Hz, 1H), 4.02 (s, 3H), 2.34 ( s, 3H), 2.15 (s, 3H), 1.63 (s, 9H), 1.62 (d, J = 7.2 Hz, 3H)
Process 5
Preparation of 2- (methoxyimino) -N- (3-methyl-1H-pyrazol-4-yl) -3- (methylthio) butanamide
A solution of 0.34 g of N- {1- (tert-butyl) -5-methyl-1H-pyrazol-4-yl} -2- (methoxyimino) -3- (methylthio) butanamide in 5 ml of formic acid was added to the reflux temperature of formic acid. For 5 hours. After completion of the reaction, 5 ml of water was added to the reaction solution and extracted with 5 ml of ethyl acetate. The obtained organic layer was washed and dried in the order of saturated brine and then anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography eluting with ethyl acetate to obtain 86 mg of the desired product as a pale yellow oil. The obtained target product was a mixture of two geometric isomers, and the isomer ratio was 3: 1.
Isomer ratio 3
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 8.21 (brs, 1H), 8.02 (s, 1H), 5.75 (brs, 1H), 4.36 (q, J = 7.2 Hz, 1H), 4.04 ( s, 3H), 2.29 (s, 3H), 2.15 (s, 3H), 1.62 (d, J = 7.2 Hz, 3H)
Isomer ratio 1
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 8.80 (brs, 1H), 8.06 (s, 1H), 5.75 (brs, 1H), 4.36 (q, J = 7.2 Hz, 1H), 4.04 ( s, 3H), 2.27 (s, 3H), 2.10 (s, 3H), 1.51 (d, J = 7.2 Hz, 3H)
Reference Example 8
Preparation of N- (3-chloro-1H-pyrazol-4-yl) -2- (methoxyimino) -3- (methylthio) butanamide
To a solution of 1 g of 2- (methoxyimino) -3- (methylthio) butanoic acid in 15 ml of dichloromethane was added 1.4 g of oxalyl chloride and then 0.2 ml of N, N-dimethylformamide at room temperature. After completion of the addition, the mixture was stirred at the same temperature for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure. The obtained residue was added at room temperature to a separately prepared solution of 0.9 g of 3-chloro-1H-pyrazol-4-amine and 1.4 g of pyridine in 20 ml of dichloromethane. After the addition was complete, stirring was continued overnight. After completion of the reaction, the solvent was distilled off from the reaction solution under reduced pressure. To the obtained residue was added 20 ml of 1N aqueous hydrochloric acid, and the mixture was extracted with 20 ml of ethyl acetate. The obtained organic layer was washed and dried in the order of saturated brine and then anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to obtain 1.2 g of the desired product as a yellow oil. The obtained target product was a mixture of two geometric isomers, and the isomer ratio was 2: 1.
Isomer ratio 2
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 9.52 (brs, 1H), 8.26 (s, 1H), 4.37-4.31 (m, 1H) 4.07 (s, 3H), 2.14 (s, 3H) ), 1.62 (d, J = 7.5 Hz, 3H)
Isomer ratio 1
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 9.52 (brs, 1H), 8.50 (s, 1H), 4.37-4.31 (m, 1H) 4.07 (s, 3H), 2.17 (s, 3H) ), 1.58 (d, J = 7.5 Hz, 3H)
Reference Example 9
Preparation of 3-methyl-1- (pyridin-3-yl) -1H-pyrazol-4-amine
Process 1
Preparation of 3-methyl-1- (pyridin-3-yl) -1H-pyrazole-4-carbonyl azide
To a solution of 500 mg of 3-methyl-1- (pyridin-3-yl) -1H-pyrazole-4-carboxylic acid in 10 ml of toluene, 0.26 g of toluethylamine and 710 mg of diphenylphosphoryl azide were sequentially added at room temperature. After completion of the addition, the reaction solution was stirred at room temperature for 5.5 hours. After completion of the stirring, 62 mg of triethylamine and 170 mg of diphenylphosphoryl azide were sequentially added again to the reaction solution. After completion of the addition, the reaction solution was continuously stirred at room temperature for 3.5 hours. After completion of the reaction, 20 ml of ethyl acetate was added to the reaction solution. After completion of the addition, the organic layer was washed and dried in the order of 2% 28% aqueous ammonia, 10 ml of water, saturated brine, and then anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained solid was washed with 5 ml of a mixed solution of n-hexane: diisopropyl ether (2: 1) to obtain 419 mg of the desired product as a white solid.
Melting point: 99-103 ° C. (decomposition)
Process 2
Preparation of 3-methyl-1- (pyridin-3-yl) -1H-pyrazol-4-amine
A 2.5 ml toluene solution of 120 mg 3-methyl-1- (pyridin-3-yl) -1H-pyrazole-4-carbonyl azide was stirred at 100 ° C. for 30 minutes. After completion of the stirring, the reaction solution was cooled to room temperature, and 1 ml of concentrated hydrochloric acid was added. After completion of the addition, the reaction solution was continuously stirred at room temperature for 10 minutes. After completion of the reaction, 10% by weight aqueous sodium hydroxide solution was added to the reaction solution to adjust the pH of the reaction solution to 11, and then extracted twice with 10 ml of ethyl acetate. The obtained organic layer was washed and dried in the order of saturated brine and anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 85 mg of the desired product as a white solid.
Melting point: 133-135 ° C
Reference Example 10
Production of (+)-2- (methoxyimino) -3- (methylthio) pentanoic acid
Process 1
Production of 2- (methoxyimino) -3- (methylthio) pentanoic acid (geometric isomer derived from the oxime structure of F-002)
28 g of oxalyl chloride and 0.5 ml of N, N-dimethylformamide were added to a solution of 35 g of 2- (methoxyimino) -3- (methylthio) pentanoic acid in 160 ml of dichloromethane. After completion of the addition, the reaction solution was stirred at room temperature for 2 hours. After completion of the reaction, the solvent of the reaction solution was distilled off under reduced pressure, and then 40 ml of tetrahydrofuran was added to the obtained residue to dissolve it. The obtained solution was added at 0 ° C. to 300 ml of a 1.5 M aqueous potassium hydroxide solution prepared separately. After completion of the addition, the reaction solution was stirred at room temperature for 3 hours. After completion of the stirring, the reaction solution was washed with 200 ml of diethyl ether, then adjusted to pH 1 with concentrated hydrochloric acid, and extracted with 300 ml of ethyl acetate. The obtained organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 33 g of the objective product as a pale yellow oil.
¹ 1 H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 4.05 (s, 3H), 4.03 (t, J = 9.0 Hz, 1H), 2.10 (s, 3H), 2.10-1.90 (m, 2H), 0.96 (t, J = 7.5Hz, 3H) (CO ₂ The proton peak of H was not observed. )
Process 2
Production of (+)-2- (methoxyimino) -3- (methylthio) pentanoic acid
To a solution of 96 g of 2- (methoxyimino) -3- (methylthio) pentanoic acid synthesized in Step 1 in 288 ml of acetonitrile, 155 g of quinidine and 768 ml of diisopropyl ether were sequentially added. After completion of the addition, the reaction solution was stirred at 65 ° C. for 5 minutes. After completion of the stirring, the reaction solution was continuously stirred at room temperature for 3 hours. After completion of the stirring, the solid precipitated in the reaction solution was filtered, and 405 ml of acetonitrile and 576 ml of diisopropyl ether were added to the obtained solid. After stirring at 65 ° C. for 5 minutes, stirring was continued at room temperature for 15 hours. . The precipitated solid was filtered, 300 ml of 1M aqueous hydrochloric acid solution was added to the obtained solid, and the mixture was extracted with 300 ml of ethyl acetate. The obtained organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 23 g of the desired product as a pale yellow oil.

Specific rotation: [α] _D ^22.0 + 35.2 ° (CHCl ₃ , c = 0.461)
Reference Example 11
Production of 3-methyl-1- (pyridin-3-yl) -1H-pyrazol-4-amine (Part 2)
Process 1
Preparation of 3-methyl-1H-pyrazol-4-amine Organic Process Research and Development 2009, Vol. 13, p. 698, 1.0 g of 3-methyl-4-nitro-1H-pyrazole synthesized according to the method described in To a 6 ml solution of tetrahydrofuran, 0.1 g of 5 wt% palladium-activated carbon was added. After completion of the addition, the reaction vessel was replaced with hydrogen gas, and then stirred overnight at room temperature. After completion of the reaction, palladium-activated carbon was removed from the reaction mixture by celite filtration. The solvent was distilled off from the obtained filtrate under reduced pressure to obtain 0.71 g of the desired product as a brown solid.
Melting point: 88-89 ° C
Process 2
Preparation of 3-methyl-1- (pyridin-3-yl) -1H-pyrazol-4-amine Into a solution of 0.61 g of 3-methyl-1H-pyrazol-4-amine in 10 ml of dimethyl sulfoxide, 1 g of 3-bromopyridine Then, 0.24 g of copper iodide (monovalent), 3.1 g of cesium carbonate, and 0.36 g of trans-N, N′-dimethylcyclohexane-1,2-diamine were sequentially added. After completion of the addition, the inside of the reaction vessel was replaced with nitrogen gas, followed by stirring at 140 ° C. for 14 hours. After completion of the reaction, the solid precipitated in the reaction mixture was filtered off. 50 ml of water was added to the obtained filtrate and extracted with 100 ml of chloroform. The obtained organic layer was washed with 50 ml of a 7 wt% aqueous ammonia solution and then with saturated saline, and then dehydrated and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane-ethyl acetate (3: 1 to 0: 1 gradient) to obtain the target product and its isomer 5- 276 mg of a mixture of methyl-1- (pyridin-3-yl) -1H-pyrazol-4-amine was obtained. This mixture was washed with diisopropyl ether to obtain the desired product (134 mg) as a brown solid.
Melting point: 125-127 ° C
Reference Example 12
Production of 3-methyl-1- (pyridin-3-yl) -1H-pyrazol-4-amine (Part 3)
To a solution of 0.61 g of 3-methyl-1H-pyrazol-4-amine in 3 ml of dimethyl sulfoxide, 1 g of 3-bromopyridine, 0.24 g of copper iodide (monovalent), 3.3 g of cesium carbonate and 2-hydroxybenzaldehyde oxime 0.35 g was added sequentially. After completion of the addition, the inside of the reaction vessel was replaced with nitrogen gas, followed by stirring at 140 ° C. for 2 hours. After completion of the reaction, the solid precipitated in the reaction mixture was filtered off. 20 ml of water was added to the obtained filtrate and extracted with 30 ml of chloroform. The obtained organic layer was washed with water and then dehydrated and dried in the order of saturated brine and anhydrous sodium sulfate. The solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel chromatography eluting with ethyl acetate to obtain 236 mg of the desired product as a pale yellow solid.
Melting point: 131-135 ° C
Reference Example 13
Production of 3-methyl-1- (pyridin-3-yl) -1H-pyrazol-4-amine (Part 4)
To a solution of 0.93 g of 3-methyl-1H-pyrazol-4-amine in 5 ml of dimethyl sulfoxide, 0.5 g of 3-bromopyridine, 0.12 g of copper iodide (monovalent) and 1.6 g of cesium carbonate were sequentially added. . After completion of the addition, the inside of the reaction vessel was replaced with nitrogen gas, followed by stirring at 140 ° C. for 7 hours. After completion of the reaction, the solid precipitated in the reaction mixture was filtered off. 50 ml of water was added to the obtained filtrate and extracted with 100 ml of chloroform. The obtained organic layer was washed with water and then dehydrated and dried in the order of saturated brine and anhydrous sodium sulfate. The solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane-ethyl acetate (3: 1 to 0: 1 gradient) to obtain 114 mg of the objective product as a yellow solid.
Melting point: 131-133 ° C
Reference Example 14
The following intermediates were synthesized using the same method as in Step 5 of Synthesis Example 1.

N- {3-chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -3- (ethylthio) -2-oxobutanamide melting point; 108-110 ° C
3- (Ethylthio) -N- {3-methyl-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -2-oxobutanamide
¹ H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 8.88 (d, J = 2.7 Hz, 1H), 8.59 (dd, J = 4.5, 1.5 Hz, 1H), 8.07 (S, 1H), 8.00-7.95 (m, 1H), 7.42 (dd, J = 8.1, 4.5 Hz, 1H), 4.10 (q, J = 6.9 Hz, 1H), 3.34 (s, 3H), 1.56 (s, 3H), 1.30 (d, J = 6.9 Hz, 3H)
N- {3-Chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -N-methyl-3- (methylthio) -2-oxobutanamide
¹ H NMR (CDCl ₃ , Me ₄ Si, 300 MHz) δ 8.98 (d, J = 2.4 Hz, 1H), 8.83 (brs, 1H), 8.72 (s, 1H), 8.60− 8.55 (m, 1H), 8.05-7.95 (m, 1H), 7.45-7.35 (m, 1H), 4.43 (q, J = 6.9 Hz, 1H), 2.65-2.40 (m, 2H), 1.52 (d, J = 7.2 Hz, 3H), 1.24 (t, J = 7.5 Hz, 3H)
N- {3-methyl-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -3- (methylthio) -2-oxobutanamide melting point; 102-104 ° C
N- {3-methyl-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -3- (methylthio) -2-oxopentanamide melting point; 94-96 ° C
This invention compound can be manufactured according to the said manufacturing method and an Example. Examples of the compounds of the present invention produced in the same manner as in Synthesis Examples 1 to 18 are shown in Tables 1 and 2 and their physical properties are shown in Table 3. However, the present invention is not limited to these. . In the table, c-Pr and Pr-c represent cyclopropyl groups, c-Hex and Hex-c represent cyclohexyl groups, and represent D1-2a, D1-7b, D1-32a, D1-32b. , D1-33a, D1-34a, D1-37a, D1-103k, D1-108a, D1-108b represent the following structures, and are described in the structural formulas of D1-7b and D1-32b. number represents the substitution position of ^{X 1,} marked by the structural formula of D1-108b numbers represent substitution position of Z.

  In the table, “* 1” represents “resin”. Further, “* 2” represents a resin-like structure having the same structure but a mixture of two isomers. If the isomer ratio is known, the ratio is listed in Table 3. “* 3” represents a geometric isomer derived from an oxime structure or a hydrazone structure. “* 4” represents a resinous structure having the same structure but a mixture of three isomers. If the isomer ratio is known, the ratio is listed in Table 3.

The symbols in Table 3 have the following meanings.
s: singlet, d: doublet, t: triplet, q: quartet, qui: quintet, sxt: sickted, sep: septette, m: multiplet, brs: broad peak.

[Table 1]

―――――――――――――――――――――――――――――――――――――
No. R ³ YR ^a R ^b-1 mp (℃)
―――――――――――――――――――――――――――――――――――――
1-001 Cl O CH ₂ CH ₃ C (= NOCH ₂ SCH ₃ ) CH ₃ 92-95
1-002 Cl O CH ₂ CH ₃ C (= NOCH ₃ ) CH (CH ₃ ) S (O) ₂ CH ₃ * 2 (~ 92: 8)
1-003 Cl O CH ₂ CH ₃ C (= NOH) CH ₃ 144-146
1-004 Cl O CH ₂ CH ₃ CH (= NOH) 152-155
1-005 Cl O CH ₂ CH ₃ C (= NOH) CH ₂ CH ₃ 111-113
1-006 Cl O CH ₂ CH ₃ C (= NOCH ₂ SCH ₃ ) CH ₂ CH ₃ 45-50
1-007 Cl O CH ₂ CH ₃ C (= NOCH ₂ CH ₂ OCH ₃ ) CH ₂ CH ₃ * 2 (~ 5: 2)
1-008 Cl O CH ₂ CH ₃ C {= NOCH ₂ CH (OCH ₃ ) ₂ } CH ₂ CH ₃ * 2 (~ 4: 1)
1-009 Cl O CH ₂ CH ₃ C (= NOCH ₃ ) (D1-34a) * 1
1-010 Cl O CH ₂ C≡CH C (= NOCH ₃ ) CH ₂ SCH ₃ * 2 (~ 7: 1)
1-011 Cl O CH ₂ C≡CH C (= NOCH ₃ ) CH ₂ S (O) CH ₃ * 1
1-012 Cl O CH ₂ C≡CH C (= NOCH ₃ ) CH ₂ S (O) ₂ CH ₃ * 1
1-013 Cl O CH ₂ CH ₃ C {= NOCH ₂ S (O) ₂ CH ₃ } CH ₃ 72-75
1-014 Cl O CH ₂ CH ₃ C (= NOCH ₂ CH ₂ OCH ₃ ) CH ₃ 60-63
1-014 (* 3) * 1
1-015 Cl OHC (= NOCH ₃ ) CH (CH ₃ ) S (O) CH ₃ 115-119
1-016 Cl O CH ₂ CH ₃ C {= NOCH ₂ CH (OCH ₃ ) ₂ } CH ₃ * 2 (~ 3: 2)
1-017 Cl O CH ₂ CH ₃ C (= NOCH ₂ CN) CH ₃ * 2 (~ 3: 2)
1-018 Cl O CH ₂ CH ₃ C (= NOCH ₃ ) (D1-32a) 114-116
1-018 (* 3) 131-133
1-019 Cl OHC (= NOCH ₃ ) CH (CH ₃ ) S (O) ₂ CH ₃ 111-113
1-020 Cl O CH ₂ CH ₃ C {= NOCH ₂ S (O) CH ₃ } CH ₃ 130-132
1-020 (* 3) * 1
1-021 Cl OHC (= NOCH ₃ ) CH ₂ S (O) CH ₃ 154-156
1-022 Cl O CH ₂ CH ₃ C {= NOC (O) CH ₃ } CH ₃ 58-60
1-023 Cl O CH ₂ CH ₃ C {= NOC (O) CH (CH ₃ ) SCH ₂ CH ₃ } CH ₃ * 2 (~ 3: 2)
1-024 Cl O CH ₂ CH ₃ C {= NOC (O) CH ₂ CH ₂ SCH ₃ } CH ₃ * 2 (~ 27: 25)
1-025 Cl O CH ₂ CH ₃ C {= NOCH ₂ C (O) NHCH ₂ CF ₃ } CH ₃ 42-46
1-026 Cl O CH ₃ C (= NOCH ₂ CH ₂ OCH ₃ ) CH ₂ S (O) CH ₃ 72-73
1-027 Cl O CH ₃ C (= NOCH ₃ ) CH ₂ S (O) CH ₃ 90-94
1-028 Cl O CH ₃ C (= NOCH ₃ ) CH ₂ S (O) ₂ CH ₃ 149-152
1-029 Cl O CH ₃ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ * 2 (~ 85: 15)
1-030 Cl O CH ₃ C (= NOCH ₃ ) CH (CH ₃ ) S (O) CH ₃ * 4 (~ 5: 4: 1)
1-031 Cl O CH ₃ C (= NOCH ₃ ) CH (CH ₃ ) S (O) ₂ CH ₃ * 2 (~ 9: 1)
1-032 Cl OHC (= NOCH ₃ ) CH ₂ SCH ₃ 108-112
1-033 Cl O CH ₂ C≡CH C (= NOCH ₃ ) (D1-103k) * 2 (~ 5: 1)
1-034 Cl O CH ₃ C (= NOCH ₂ CH ₃ ) CH ₂ SCH ₃ * 1
1-035 Cl O CH ₂ CH ₃ C (= NOCH ₂ CH ₂ SCH ₃ ) CH ₃ 40-45
1-036 Cl O CH ₂ CH ₃ C {= NOCH ₂ C (O) OCH ₂ CH ₃ } CH ₃ 52-57
1-037 Cl O CH ₃ C (= NOCH ₂ CH ₃ ) CH ₂ S (O) CH ₃ * 2 (~ 4: 1)
1-038 Cl O CH ₃ C (= NOCH ₂ CH ₃ ) CH ₂ S (O) ₂ CH ₃ 87-91
1-039 Cl O CH ₃ C (= NOCH ₂ Pr-c) CH ₂ S (O) CH ₃ 128-130
1-040 Cl O CH ₃ C (= NOCH ₂ Pr-c) CH ₂ S (O) ₂ CH ₃ 155-157
1-041 Cl O CH ₂ CH ₃ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ 72-74
1-042 Cl O CH ₂ CH ₃ C (= NOCH ₃ ) CH (CH ₃ ) S (O) CH ₃ * 2 (~ 3: 2)
1-043 Cl O CH ₂ OCH ₃ C (= NOCH ₃ ) CH ₂ SCH ₃ * 1
1-044 Cl O CH ₂ OCH ₃ C (= NOCH ₃ ) CH ₂ S (O) ₂ CH ₃ * 2 (~ 85: 15)
1-045 Cl O CH ₂ OCH ₂ CH ₃ C (= NOCH ₃ ) CH ₂ SCH ₃ * 1
1-046 Cl O CH ₂ CN C (= NOCH ₃ ) CH ₂ SCH ₃ * 2 (~ 92: 8)
1-047 Cl O CH ₃ C (= NOCH ₂ Pr-c) CH ₂ SCH ₃ * 1
1-048 Cl O CH ₃ C (= NOCH ₂ CH ₂ OCH ₃ ) CH ₂ SCH ₃ * 1
1-049 Cl O CH ₃ C (= NOCH ₂ CH ₂ OCH ₃ ) CH ₂ S (O) ₂ CH ₃ 106-107
1-050 Cl O CH ₃ C (= NOCH ₂ SCH ₃ ) CH ₂ SCH ₃ * 1
1-051 Cl O CH ₃ C (= NOCH ₂ CH ₂ SCH ₃ ) CH ₂ SCH ₃ * 1
1-052 Cl O CH ₃ C (= NOCH ₂ OCH ₃ ) CH ₂ SCH ₃ 85-89
1-053 Cl O CH ₃ C (= NOCH ₂ OCH ₃ ) CH ₂ S (O) CH ₃ * 1
1-054 Cl O CH ₃ C (= NOCH ₃ ) C (O) CH ₃ * 2 (~ 3: 2)
1-055 Cl O CH ₃ C (= NOCH ₂ OCH ₃ ) CH ₂ S (O) ₂ CH ₃ * 2 (~ 50: 7)
1-056 Cl O CH ₂ CN C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ * 1
1-056 (* 3) * 2 (~ 81: 19)
1-056-(+) 97.1% ee [α] _D ^23.6 + 34.88 ° (CHCl ₃ , c = 0.734)
1-056-(-) 99% ee [α] _D ^23.5 -41.23 ° (CHCl ₃ , c = 0.624)
1-057 Cl OHC (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ 80-82
1-057 (* 3) * 1
1-057-(+) 90.2% ee [α] _D ^23.3 + 36.92 ° (CHCl ₃ , c = 0.104)
1-057-(-) 99% ee [α] _D ^23.2 -42.84 ° (CHCl ₃ , c = 0.116)
1-058 Cl O CH ₂ SCH ₃ C (= NOCH ₃ ) CH ₂ SCH ₃ * 1
1-059 Cl O CH ₂ CH = CH ₂ C (= NOCH ₃ ) CH ₂ SCH ₃ * 1
1-060 Cl O CH ₃ C (= NOPr-i) CN * 1
1-061 Cl OHC (= NOCH ₂ CH ₂ OCH ₃ ) CH ₂ SCH ₃ 75-78
1-062 Cl OHC (= NOCH ₃ ) CH ₂ S (O) ₂ CH ₃ 169-171
1-063 Cl O CH ₂ CN C (= NOCH ₃ ) CH ₂ S (O) ₂ CH ₃ 122-124
1-064 Cl O CH ₂ C≡CH C (= NOCH ₃ ) C {S (O) ₂ CH ₃ } = CH ₂ 133-134
1-065 Cl O CH ₂ Pr-c C (= NOCH ₃ ) CH ₂ SCH ₃ * 1
1-066 Cl O CH (CH ₃ ) OCH ₃ C (= NOCH ₃ ) CH ₂ SCH ₃ * 2 (~ 87: 13)
1-067 Cl O CH ₂ (D1-108a) C (= NOCH ₃ ) CH ₂ SCH ₃ * 1
1-068 Cl OC (O) OCH ₃ C (= NOCH ₃ ) CH ₂ SCH ₃ * 2 (~ 5: 1)
1-069 Cl O CH ₂ (D1-108b, 2-Cl) C (= NOCH ₃ ) CH ₂ SCH ₃ * 1
1-070 Cl O CH ₂ (D1-108b, 3-Cl) C (= NOCH ₃ ) CH ₂ SCH ₃ * 1
1-071 Cl O CH ₂ (D1-108b, 4-Cl) C (= NOCH ₃ ) CH ₂ SCH ₃ * 1
1-072 Cl O CH ₂ C (O) OCH ₃ C (= NOCH ₃ ) CH ₂ SCH ₃ 83-86
1-073 Cl O CH ₂ OC (O) CH ₃ C (= NOCH ₃ ) CH ₂ SCH ₃ * 1
1-074 Cl O CH (CH ₃ ) CN C (= NOCH ₃ ) CH ₂ SCH ₃ * 2 (~ 5: 1)
1-075 Cl O CH (CH ₃ ) OCH ₃ C (= NOCH ₃ ) CH ₂ S (O) CH ₃ * 2 (~ 1: 1)
1-076 Cl O CH (CH ₃ ) OCH ₃ C (= NOCH ₃ ) CH ₂ S (O) ₂ CH ₃ 125-127
1-077 Cl O CH ₂ OCH ₃ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ * 1
1-077 (* 3) * 2 (~ 5: 1)
1-078 Cl O CH ₃ C (= NOCH ₃ ) SCH ₂ CH ₃ 135-138
1-079 Cl O CH (CH ₃ ) CN C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ * 1
1-080 Cl O CH ₃ C (= NOCH ₃ ) CH ₂ CH ₂ SCH ₃ * 2 (~ 1: 1)
1-081 Cl O CH ₂ OCH ₂ (D1-108a) C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ * 1
1-082 Cl O CH ₂ CN C (= NOCH ₃ ) CH (CH ₃ ) S (O) CH ₃ * 2 (~ 3: 2)
1-083 Cl O CH ₂ CN C (= NOCH ₃ ) CH (CH ₃ ) S (O) ₂ CH ₃ 144-147
1-084 Cl O CH ₂ OC (O) CH ₃ C (= NOCH ₃ ) CH ₂ S (O) ₂ CH ₃ * 1
1-085 Cl O CH (CH ₃ ) OC (O) OCH ₂ CH ₃ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ * 2 (~ 4: 1)
1-086 Cl O CH ₂ OC (O) C (CH ₃ ) ₃ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ * 1
1-087 Cl O CH ₂ OC (O) CH ₃ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ * 1
1-088 Cl O CH ₂ OC (O) CH ₃ C (= NOCH ₃ ) CH (CH ₃ ) S (O) ₂ CH ₃ * 2 (~ 20: 13)
1-089 Cl O CH ₂ OCH ₂ CH ₂ OCH ₃ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ * 1
1-090 Cl O CH ₂ OCH ₃ C (= NOCH ₃ ) CH (CH ₃ ) S (O) CH ₃ * 2 (~ 4: 1)
1-090 (* 3) * 2 (~ 6: 1)
1-091 Cl O CH ₂ OCH ₃ C (= NOCH ₃ ) CH (CH ₃ ) S (O) ₂ CH ₃ * 1
1-091 (* 3) 37-40
1-092 Cl O CH ₂ OCH ₂ (D1-108a) C (= NOCH ₃ ) CH (CH ₃ ) S (O) ₂ CH ₃ * 2 (~ 4: 3)
1-093 Cl O CH ₂ OCH ₂ (D1-108a) C (= NOCH ₃ ) CH (CH ₃ ) S (O) CH ₃ * 1
1-094 Cl O CH ₂ OCH ₂ CH ₂ Si (CH ₃ ) ₃ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ * 1
1-095 Cl O CH ₂ OC (O) (D1-108a) C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ * 1
1-096 Cl O CH ₂ OC (O) CH ₂ CH ₂ CH ₃ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ * 1
1-097 Cl O CH ₂ OCH ₂ CH ₃ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ 47-49
1-098 Cl O CH ₂ OCH ₂ CH ₃ C (= NOCH ₃ ) CH (CH ₃ ) S (O) ₂ CH ₃ * 1
1-099 Cl OS (O) ₂ CH ₃ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ * 1
1-100 Cl O CH ₂ C (O) NH ₂ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ * 1
1-101 Cl O CH ₂ C (O) OCH ₂ CH ₃ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ 66-68
1-102 Cl OC (O) OCH ₃ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ * 1
1-103 Cl OHC (= NOCH ₃ ) CH (CH ₃ ) SCH ₂ CH ₃ 64-67
1-104 Cl O CH ₂ CN C (= NOCH ₃ ) CH (CH ₃ ) SCH ₂ CH ₃ * 2 (~ 95: 5)
1-105 Cl O CH ₂ OC (O) OCH ₃ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ 58-61
1-105 (* 3) * 2 (~ 2: 1)
1-106 Cl O CH ₂ OCH (CH ₃ ) ₂ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ 55-57
1-107 Cl O CH ₂ OCH ₂ C≡CH C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ 79-81
1-108 Cl O CH ₂ C (O) N (CH ₂ CH ₃ ) ₂ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ 80-82
1-109 Cl O CH ₂ C (O) OH C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ 209-213
1-110 Cl O CH ₂ C (O) NHCH ₂ CH ₃ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ 142-144
1-111 Cl OC (O) NHCH ₂ CH ₃ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ 46-49
1-112 Cl O CH ₂ OC (O) N (CH ₂ CH ₃ ) ₂ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ * 2 (~ 50: 6)
1-113 Cl O CH (CH ₃ ) OCH ₃ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ * 2 (~ 83: 10)
1-114 Cl O CH ₂ SCH ₃ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ * 1
1-115 Cl O CH (CH ₃ ) OCH ₂ CH ₃ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ * 2 (~ 83: 17)
1-116 CH ₃ OHC (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ 72-75
1-116 (* 3) * 1
1-116-(+) 94.5% ee [α] _D ^24.7 + 37.0 ° (CHCl ₃ , c = 0.443)
1-116-(-) 99% ee [α] _D ^22.8 -45.60 ° (CHCl ₃ , c = 0.120)
1-117 Cl O CH ₂ OC (O) OCH ₂ CH ₃ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ 51-64
1-118 Cl O CH ₂ OC (O) OCH ₂ CH ₂ OCH ₃ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ * 1
1-119 Cl O CH ₂ OC (O) OCH ₂ CH ₂ OCH ₃ C (= NOCH ₃ ) CH (CH ₃ ) S (O) ₂ CH ₃ * 1
1-120 Cl OC (S) NHCH ₃ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ * 2 (~ 87: 13)
1-121 Cl OHC (= NOCH ₃ ) CH (CH ₂ CH ₃ ) SCH ₃ 62-63
1-122 Cl OHC (= NOCH ₃ ) CH {CH (CH ₃ ) ₂ } SCH ₃ * 2 (~ 93: 7)
1-123 HOHC (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ 110-120
1-124 Cl O CH ₂ OC (O) OCH ₃ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₂ CH ₃ 46-49
1-125 CH ₃ O CH ₂ OC (O) OCH ₃ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ 86-88
1-126 Cl O CH ₂ OC (O) OCH ₃ C (= NOCH ₃ ) CH (CH ₃ ) S (O) ₂ CH ₂ CH ₃ 83-86
1-127 Cl O CH ₂ OC (O) OCH ₃ C (= NOCH ₃ ) CH (CH ₂ CH ₃ ) SCH ₃ 69-70
1-128 HO CH ₂ OC (O) OCH ₃ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ * 1
1-129 HO CH ₂ OC (O) OCH ₃ C (= NOCH ₃ ) CH (CH ₃ ) S (O) ₂ CH ₃ * 1
1-130 Cl O CH ₂ OC (O) OCH ₃ C (= NOCH ₃ ) CH (CH ₃ ) S (O) ₂ CH ₃ 113-116
1-131 Cl OHC (= NOCH ₂ CH ₃ ) CH (CH ₃ ) SCH ₃ 64-67
1-132 Cl O CH ₂ OC (O) OCH ₃ C (= NOCH ₃ ) CH {CH (CH ₃ ) ₂ } SCH ₃ * 2 (~ 3: 1)
1-133 CH ₃ O CH ₂ OC (O) OCH ₃ C (= NOCH ₃ ) CH (CH ₃ ) S (O) ₂ CH ₃ 125-127
1-134 Cl O CH ₂ OC (O) OCH ₃ C (= NOCH ₂ CH ₃ ) CH (CH ₃ ) SCH ₃ 52-54
1-135 CH ₃ OHC (= NOCH ₃ ) CH (CH ₃ ) SCH ₂ CH ₃ 69-71
1-136 CH ₃ OHC (= NOCH ₃ ) CH (CH ₃ ) S (O) CH ₃ 118-127
1-137 CH ₃ OHC (= NOCH ₃ ) CH (CH ₃ ) S (O) ₂ CH ₃ 124-129
1-138 CH ₃ OHC (= NOCH ₃ ) CH (CH ₃ ) S (O) CH ₂ CH ₃ 88-110
1-139 CH ₃ OHC (= NOCH ₃ ) CH (CH ₃ ) S (O) ₂ CH ₂ CH ₃ 138-143
1-140 Cl OHC (= NOCH ₂ CH ₃ ) CH (CH ₃ ) SCH ₂ CH ₃ 55-60
1-141 CH ₃ OHC (= NOCH ₃ ) CH (CH ₂ CH ₃ ) SCH ₃ 80-84
1-141-(+) 85% ee [α] _D ^23.0 + 12.03 ° (CHCl ₃ , c = 0.142) 93-94
1-141-(-) 99% ee [α] _D ^22.9 -46.11 ° (CHCl ₃ , c = 0.110) 96-97
1-142 CH ₃ O CH ₂ OC (O) CH ₃ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₂ CH ₃ * 1
1-143 CH ₃ O CH ₂ OC (O) OCH ₃ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₂ CH ₃ * 1
1-144 CH ₃ O CH ₂ OCH ₃ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ * 2 (~ 5: 1)
1-145 CH ₃ OC (O) C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₂ CH ₃ * 1
1-146 Cl OHC (= NOCH ₃ ) (D1-2a) 114-116
1-147 CH ₃ O CH ₃ C (= NOCH ₃ ) CH (CH ₂ CH ₃ ) SCH ₃ 62-64
1-148 CH ₃ O CH ₃ C (= NOCH ₃ ) CH (CH ₂ CH ₃ ) S (O) CH ₃ * 2 (~ 2: 1)
1-149 CH ₃ O CH ₃ C (= NOCH ₃ ) CH (CH ₂ CH ₃ ) S (O) ₂ CH ₃ * 2 (~ 25: 3)
1-150 Cl O CH ₃ C (= NOCH ₃ ) CH (CH ₂ CH ₃ ) SCH ₃ 65-67
1-151 CH ₃ O CH ₃ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ 50-52
1-152 Cl O CH ₂ (D1-33a) C (= NOCH ₃ ) CH (CH ₃ ) SCH ₂ CH ₃ 110-113
1-153 Cl O CH ₂ (D1-34a) C (= NOCH ₃ ) CH (CH ₃ ) SCH ₂ CH ₃ * 1
1-154 CH ₃ OHC (= NOCH ₃ ) CH (CH ₂ CH ₃ ) S (O) CH ₃ * 2 (~ 8: 7)
1-155 CH ₃ OHC (= NOCH ₃ ) CH (CH ₂ CH ₃ ) S (O) ₂ CH ₃ * 1
1-156 CH ₃ OHC (= NOCH ₃ ) CH (CH ₂ OCH ₃ ) SCH ₃ * 1
1-157 Cl O CH ₂ (D1-32a) C (= NOCH ₃ ) CH (CH ₃ ) SCH ₂ CH ₃ 80-82
1-158 CH ₃ O CH ₃ C (= NOCH ₃ ) CH (CH ₃ ) S (O) CH ₃ 34-35
1-159 CH ₃ O CH ₃ C (= NOCH ₃ ) CH (CH ₃ ) S (O) ₂ CH ₃ 42-43
1-160 CH ₃ O CH ₂ OC (O) CH ₃ C (= NOCH ₃ ) CH (CH ₂ CH ₃ ) SCH ₃ * 1
1-161 CH ₃ O CH ₂ OC (O) OCH ₃ C (= NOCH ₃ ) CH (CH ₂ CH ₃ ) SCH ₃ 64-65
1-162 CH ₃ OHC (= NOCH ₃ ) CH (CH ₂ OCH ₃ ) S (O) ₂ CH ₃ * 1
1-163 CH ₃ O CH ₂ OCH ₂ CH ₃ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ * 1
1-164 CH ₃ O CH ₂ OC (O) OCH ₃ C (= NOCH ₃ ) CH (CH ₂ OCH ₃ ) SCH ₃ * 1
1-165 CH ₃ O CH ₂ OC (O) OCH ₃ C (= NOCH ₃ ) CH (CH ₂ OCH ₃ ) S (O) CH ₃ * 1
1-166 CH ₃ O CH ₂ OC (O) OCH ₃ C (= NOCH ₃ ) CH (CH ₂ OCH ₃ ) S (O) ₂ CH ₃ * 1
1-167 CH ₃ O CH ₂ OC (O) OCH ₃ C (= NOCH ₃ ) CH (CH ₂ CH ₃ ) S (O) CH ₃ * 2 (~ 3: 2)
1-168 CH ₃ O CH ₂ OC (O) OCH ₃ C (= NOCH ₃ ) CH (CH ₂ CH ₃ ) S (O) ₂ CH ₃ * 1
1-169 CH ₃ O CH ₂ OC (O) CH ₃ C (= NOCH ₃ ) CH (CH ₂ CH ₃ ) S (O) CH ₃ 126-127
1-170 CH ₃ O CH ₂ OC (O) CH ₃ C (= NOCH ₃ ) CH (CH ₂ CH ₃ ) S (O) ₂ CH ₃ * 1
1-171 CH ₃ O CH ₂ CN C (= NOCH ₃ ) CH (CH ₂ CH ₃ ) SCH ₃ * 1
1-172 CH ₃ O CH ₂ OCH ₂ CH ₃ C (= NOCH ₃ ) CH (CH ₃ ) S (O) CH ₃ * 1
1-173 CH ₃ O CH ₂ OCH ₂ CH ₃ C (= NOCH ₃ ) CH (CH ₃ ) S (O) ₂ CH ₃ * 4 (~ 58: 27: 15)
1-174 CH ₃ O CH ₂ CN C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ * 1
1-175 CH ₃ O CH ₂ CN C (= NOCH ₃ ) CH (CH ₃ ) S (O) CH ₃ * 2 (~ 5: 3)
1-176 CH ₃ O CH ₂ CN C (= NOCH ₃ ) CH (CH ₃ ) S (O) ₂ CH ₃ * 1
1-177 CH ₃ O CH ₂ CN C (= NOCH ₃ ) CH (CH ₂ CH ₃ ) S (O) CH ₃ * 1
1-178 CH ₃ O CH ₂ CN C (= NOCH ₃ ) CH (CH ₂ CH ₃ ) S (O) ₂ CH ₃ * 1
1-179 CH ₃ O CH ₂ OC (O) CH ₃ C (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ * 2 (~ 10: 1)
1-180 CH ₃ O CH ₂ OC (O) CH ₃ C (= NOCH ₃ ) CH (CH ₃ ) S (O) CH ₃ * 1
1-181 CH ₃ O CH ₂ OC (O) CH ₃ C (= NOCH ₃ ) CH (CH ₃ ) S (O) ₂ CH ₃ * 1
1-182 CH ₃ O CH ₂ OC (O) OCH ₃ C (= NOCH ₃ ) CH (CH ₃ ) S (O) CH ₃ * 1
1-183 CH ₃ O CH ₂ CN C (= NOCH ₂ CH ₃ ) CH (CH ₃ ) SCH ₃ * 1
1-184 CH ₃ O CH ₂ CN C (= NOCH ₂ CH ₂ OCH ₃ ) CH ₂ SCH ₃ * 1
1-185 CH ₃ O CH ₂ OCH ₂ CH ₃ C (= NOCH ₃ ) CH (CH ₂ CH ₃ ) SCH ₃ * 1
1-186 Cl O CH ₃ C (= NOH) CH (CH ₃ ) SCH ₃ 163-165
1-187 CH ₃ O CH ₂ OCH ₂ CH ₃ C (= NOCH ₃ ) CH (CH ₂ CH ₃ ) S (O) CH ₃ * 1
1-188 CH ₃ O CH ₂ OCH ₂ CH ₃ C (= NOCH ₃ ) CH (CH ₂ CH ₃ ) S (O) ₂ CH ₃ 99-100
1-189 CH ₃ O CH ₂ OCH ₃ C (= NOCH ₃ ) CH (CH ₂ CH ₃ ) S (O) CH ₃ * 1
1-190 CH ₃ O CH ₂ OCH ₃ C (= NOCH ₃ ) CH (CH ₂ CH ₃ ) S (O) ₂ CH ₃ * 2 (~ 2: 1)
1-191 CH ₃ O CH ₂ OCH ₃ C (= NOCH ₃ ) CH (CH ₃ ) S (O) ₂ CH ₃ * 4 (~ 51: 25: 24)
1-192 CH ₃ O CH ₂ OCH ₃ C (= NOCH ₃ ) CH (CH ₂ CH ₃ ) SCH ₃ * 1
1-193 Cl OHC (= NOCH ₃ ) CH ₂ {D1-7b (3-CF ₃ )} 133-136
1-194 Cl O CH ₃ C (= NOCH ₂ CN) CH (CH ₃ ) SCH ₃ * 1
1-195 Cl O CH ₃ C {= NOC (O) OCH ₃ } CH (CH ₃ ) SCH ₃ * 1
1-196 Cl O CH ₃ C {= NOC (O) CH ₃ } CH (CH ₃ ) SCH ₃ * 1
1-197 CH ₃ OHC (= NOCH ₃ ) C (CH ₃ ) ₂ SCH ₃ * 1
1-198 Cl O CH ₃ C (= NOCH ₂ OCH ₃ ) CH (CH ₃ ) SCH ₃ * 1
1-199 Br OHC (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ 85-88
1-200 CH ₃ OHC (= NOCH ₃ ) C (CH ₃ ) ₂ S (O) ₂ CH ₃ * 1
1-201 CH ₃ OHC (= NOCH ₃ ) CH ₂ SCH ₃ 97-102
1-202 CH ₃ OHC (= NOCH ₃ ) CH ₂ S (O) ₂ CH ₃ 167-170
1-203 CH ₃ OHC (= NOCH ₃ ) CH (CH ₂ CH ₃ ) OS (O) ₂ {D1-108b (Z = 4-CH ₃ )} * 1
1-204 CH ₃ OHC (= NOCH ₃ ) CH (CH ₂ CH ₃ ) Cl 105-107
1-205 CH ₃ OHC (= NOCH ₃ ) CH (CH ₂ CH ₃ ) S {D1-32b (3-CF ₃ )} * 1
1-206 CH ₃ SHC (= NOCH ₃ ) CH (CH ₃ ) SCH ₃ 73-76
1-207 CH ₃ OHC (= NOCH ₃ ) (D1-108a) * 2 (~ 2: 1)
1-208 Cl OC (O) CH (CH ₃ ) SCH ₃ C (= NOCH ₃ ) CH ₃ * 1
1-209 CH ₃ OHC (= NOCH ₃ ) CH (CH ₂ CH ₃ ) SCH ₂ CF ₃ 70-72
1-210 Cl O CH ₂ CH ₃ C {= NNHS (O) ₂ CH ₃ } CH ₃ 41-44
1-211 CH ₃ OHC {= NNHC (O) CH ₃ } CH (CH ₂ CH ₃ ) SCH ₃ 138-142
1-212 CH ₃ OHC (= NNHCH ₂ CH ₃ ) CH (CH ₂ CH ₃ ) SCH ₃ * 1
1-213 CH ₃ OHC {= NNHC (O) OCH ₃ } CH (CH ₂ CH ₃ ) SCH ₃ 144-146
1-214 CH ₃ OHC {= NNH (D1-37a)} CH (CH ₃ ) SCH ₃ 49-51
1-215 Cl O CH ₃ C {= NNH (D1-37a)} CH ₃ 39-41
1-216 CH ₃ OHC {= NNH (D1-37a)} CH (CH ₃ ) S (O) ₂ CH ₃ 191-194
1-217 CH ₃ OHC (= NNHCH ₂ CF ₃ ) CH (CH ₂ CH ₃ ) SCH ₃ 133-135
1-217 (* 3) 61-64
1-218 CH ₃ OHC {= NNH (D1-108a)} CH (CH ₂ CH ₃ ) SCH ₃ * 1
1-219 CH ₃ OHC (= NNH ₂ ) CH (CH ₂ CH ₃ ) SCH ₃ 127-130
1-220 CH ₃ OHC {= NNHC (O) H} CH (CH ₃ ) SCH ₃ 41-44
1-221 Cl OHC {= NNHC (O) OC (CH ₃ ) ₃ } CH (CH ₃ ) SCH ₃ 49-50
1-222 Cl OHC {= NNHCH ₂ CH = CH ₂ } CH (CH ₃ ) SCH ₃ * 1
1-223 CH ₃ OHC (= NOCH ₃ ) CH (CH ₂ CH ₃ ) OCH ₃ 90-92
1-224 Cl OHC (= NOCH ₃ ) {D1-108b (4-Cl)} 214-215
1-225 CH ₃ OHC (= NOCH ₃ ) CH (CH ₂ CH ₃ ) SCH ₂ CH = CH ₂ * 2 (~ 3: 1)
1-226 CH ₃ OHC (= NOH) CH (CH ₃ ) SCH ₃ 207-210
1-227 Cl OH CH [= NNHC (O) NH {D1-108b (2,6-Cl ₂ )}] 211-214
1-228 CH ₃ OHC {= NNHC (O) CH ₃ } CH (CH ₃ ) SCH ₃ 154-156
1-228 (* 3) 116-118
1-229 Cl OHC {= NNHC (O) CH ₃ } CH (CH ₃ ) SCH ₃ 154-156
1-230 CH ₃ OC (O) Pr-c C [= NNHC (O) Pr-c] CH (CH ₃ ) SCH ₃ 59-61
1-231 CH ₃ OHC {= NNHC (O) OCH ₂ (D1-108a)} CH (CH ₃ ) SCH ₃ * 1
1-231 (* 3) 103-105
――――――――――――――――――――――――――――――――――――――
[Table 2]

―――――――――――――――――――――――――――――――――――――
No. R ^Three A ² R ^a R ^b-1 mp (℃)
―――――――――――――――――――――――――――――――――――――
2-001 Cl CF HC (= NOCH _Three ) CH (CH _Three ) SCH _Three 97-99
2-002 Cl CF CH ₂ OC (O) OCH _Three C (= NOCH _Three ) CH (CH _Three ) SCH _Three 49-50
2-003 CH _Three CF HC (= NOCH _Three ) CH (CH _Three ) SCH _Three 130-131
2-004 CH _Three NHC (= NOCH _Three ) CH (CH _Three ) SCH _Three 116-118
―――――――――――――――――――――――――――――――――――――
[Table 3]
―――――――――――――――――――――――――――――――――――――――
No.
Proton nuclear magnetic resonance chemical shift value (CDCl ₃ Middle): σ (ppm)
―――――――――――――――――――――――――――――――――――――――
1-002;
(Isomer ratio 92) 9.02-8.92 (m, 1H), 8.63-8.56 (m, 1H), 8.09 (s, 1H), 8.05-7.94 (m , 1H), 7.47-7.38 (m, 1H), 4.62 (q, J = 7.2 Hz, 1H), 3.95 (dq, J = 13.8, 6.9 Hz, 1H) 3.77 (s, 3H), 3.56 (dq, J = 13.8, 6.6 Hz, 1H), 2.94 (s, 3H), 1.76 (d, J = 7.2 Hz, 3H), 1.30-1.19 (m, 3H)
(Isomer ratio 8) 9.02-8.92 (m, 1H), 8.63-8.56 (m, 1H), 8.09 (s, 1H), 8.05-7.94 (m , 1H), 7.47-7.38 (m, 1H), 4.90-4.78 (m, 1H), 3.95 (dq, J = 13.8, 6.9 Hz, 1H), 3 .77 (s, 3H), 3.56 (dq, J = 13.8, 6.6 Hz, 1H), 3.02 (s, 3H), 1.76 (d, J = 7.2 Hz, 3H) , 1.30-1.19 (m, 3H)
1-007;
(Isomer ratio 5) 9.06 (d, J = 2.4 Hz, 1H), 8.77 (s, 1H), 8.58 (dd, J = 4.8, 1.2 Hz, 1H), 8 .12 (ddd, J = 8.4, 2.4, 1.2 Hz, 1H), 7.42 (dd, J = 8.4, 4.8 Hz, 1H), 4.30-4.10 (m , 4H), 3.75-3.65 (m, 2H), 3.43 (s, 3H), 2.35-2.20 (m, 2H), 1.18 (t, J = 7.2 Hz). , 3H), 1.04 (t, J = 7.2 Hz, 3H)
(Isomer ratio 2) 8.92 (d, J = 2.4 Hz, 1H), 8.65-8.55 (m, 1H), 8.05-7.95 (m, 1H), 7.87 (S, 1H), 7.42 (dd, J = 8.4, 4.8 Hz, 1H), 4.03 (t, J = 5.1 Hz, 2H), 3.80 (q, J = 7. 2 Hz, 2H), 3.75-3.60 (m, 2H), 3.20 (s, 3H), 2.47 (q, J = 7.2 Hz, 2H), 1.22 (t, J = 7.2 Hz, 3H), 1.08 (t, J = 7.2 Hz, 3H)
1-008;
(Isomer ratio 4) 9.08 (d, J = 2.4 Hz, 1H), 8.68 (s, 1H), 8.59 (dd, J = 4.8, 1.2 Hz, 1H), 8 .13 (ddd, J = 8.4, 2.4, 1.2 Hz, 1H), 7.42 (dd, J = 8.4, 4.8 Hz, 1H), 4.68 (t, J = 5 .4 Hz, 1H), 4.30-4.00 (m, 4H), 3.44 (s, 3H), 3.34 (s, 3H), 2.30-2.15 (m, 2H), 1.18 (t, J = 7.2 Hz, 3H), 1.03 (t, J = 7.2 Hz, 3H)
(Isomer ratio 1) 8.94 (d, J = 2.4 Hz, 1H),
8.46 (dd, J = 4.8, 1.2 Hz, 1H), 8.00-7.90 (m, 1H), 7.42 (dd, J = 8.4, 4.8 Hz, 1H) 7.34 (s, 1H), 4.30-3.80 (m, 5H), 3.50-3.30 (m, 3H), 3.22 (s, 3H), 2.30-2 .15 (m, 2H), 1.30-1.20 (m, 6H)
1-009;
9.00-8.70 (m, 2H), 8.61 (dd, J = 4.8, 1.5 Hz, 2H), 7.89 (ddd, J = 8.4, 2.7, 1. 5 Hz, 1 H), 7.68 (s, 1 H), 7.40 (dd, J = 8.4, 4.8 Hz, 1 H), 7.32 (dd, J = 4.8, 1.5 Hz, 2 H ), 3.89 (s, 3H), 3.82 (q, J = 7.2 Hz, 2H), 1.24 (t, J = 7.2 Hz, 3H)
1-010;
(Isomer ratio 7) 8.92 (d, J = 2.7 Hz, 1H), 8.60 (dd, J = 4.8, 1.2 Hz, 1H), 8.09 (s, 1H), 8 .02 (ddd, J = 8.7, 2.7, 1.2 Hz, 1H), 7.44 (dd, J = 8.7, 4.8 Hz, 1H), 4.60-4.40 (m , 2H), 3.70 (s, 3H), 3.55 (s, 2H), 2.28 (t, J = 2.4 Hz, 1H), 1,93 (s, 3H)
(Isomer ratio 1) 8.92 (d, J = 2.7 Hz, 1H), 8.60 (dd, J = 4.8, 1.2 Hz, 1H), 8.09 (s, 1H), 8 .02 (ddd, J = 8.7, 2.7, 1.2 Hz, 1H), 7.44 (dd, J = 8.7, 4.8 Hz, 1H), 4.80-4.60 (m , 2H), 4.08 (s, 3H), 3.56 (s, 2H), 2.28 (t, J = 2.4 Hz, 1H), 2.15 (s, 3H)
1-011;
8.98 (d, J = 2.7 Hz, 1H), 8.58 (dd, J = 4.8, 1.5 Hz, 1H), 8.26 (s, 1H), 8.01 (ddd, J = 8.1, 2.7, 1.5 Hz, 1H), 7.41 (dd, J = 8.1, 4.8 Hz, 1H), 4.60-4.40 (m, 2H), 4. 08 (d, J = 12.3 Hz, 1H), 3.95 (d, J = 12.3 Hz, 1H), 3.78 (s, 3H), 2.59 (s, 3H), 2.28 ( t, J = 2.4 Hz, 1H)
1-012;
8.97 (d, J = 2.7 Hz, 1H), 8.59 (dd, J = 4.8, 1.2 Hz, 1H), 8.16 (s, 1H), 7.98 (ddd, J = 8.1, 2.7, 1.2 Hz, 1H), 7.41 (dd, J = 8.1, 4.8 Hz, 1H), 4.60-4.40 (m, 4H), 3. 82 (s, 3H), 2.88 (s, 3H), 2.29 (t, J = 2.4 Hz, 1H)
1-014 (* 3);
8.92 (d, J = 2.7 Hz, 1H), 8.60 (dd, J = 4.8 Hz, 1.2 Hz, 1H), 8.01 (ddd, J = 8.4, 2.7, 1.2 Hz, 1H), 7.88 (s, 1H), 7.43 (dd, J = 8.4, 4.8 Hz, 1H), 4.02 (t, J = 4.8 Hz, 2H), 3.77 (q, J = 7.2 Hz, 2H), 3.36 (t, J = 4.8 Hz, 2H), 3.19 (s, 3H), 1.99 (s, 3H), 1. 22 (t, J = 7.2Hz, 3H)
1-016;
(Isomer ratio 3) 9.08 (d, J = 2.7 Hz, 1H), 8.66 (s, 1H), 8.65-8.55 (m, 1H), 8.20-8.10 (M, 1H), 7.50-7.40 (m, 1H), 4.66 (t, J = 5.4 Hz, 1H), 4.20-4.00 (m, 2H), 3.89 (D, J = 5.4 Hz, 2H), 3.41 (s, 6H), 1.89 (s, 3H), 1.30-1.15 (m, 3H)
(Isomer ratio 2) 8.94 (d, J = 2.7 Hz, 1H), 8.65-8.55 (m, 1H), 8.20-8.10 (m, 1H), 7.89 (S, 1H), 7.50-7.40 (m, 1H), 4.30-4.20 (m, 1H), 3.78 (q, J = 7.2 Hz, 2H), 3.89 (D, J = 5.4 Hz, 2H), 3.21 (s, 6H), 1.99 (s, 3H), 1.30-1.15 (m, 3H)
1-017;
(Isomer ratio 3) 9.04 (d, J = 2.7 Hz, 1H), 8.65-8.55 (m, 1H), 8.15-8.00 (m, 2H), 7.50 −7.35 (m, 1H), 4.72 (s, 2H), 3.79 (q, J = 7.2 Hz, 2H), 1.98 (s, 3H), 1.20 (t, J = 7.2Hz, 3H)
(Isomer ratio 2) 8.98 (d, J = 2.7 Hz, 1H), 8.65-8.55 (m, 1H), 8.15-8.00 (m, 1H), 7.98 (S, 1H), 7.50-7.35 (m, 1H), 4.55 (s, 2H), 3.79 (q, J = 7.2 Hz, 2H), 2.01 (s, 3H) ), 1.26 (t, J = 7.2 Hz, 3H)
1-018;
8.70-8.60 (m, 1H), 8.57 (d, J = 3.0 Hz, 1H), 8.52 (dd, J = 4.8, 1.2 Hz, 1H), 7.83 (S, 1H), 7.82 (ddd, J = 8.4, 3.0, 1.2 Hz, 1H), 7.75-7.60 (m, 2H), 7.34 (dd, J = 8.4, 4.8 Hz, 1H), 7.30-7.20 (m, 1H), 4.20-4.05 (m, 2H), 4.00 (s, 3H), 1.26 ( t, J = 7.2 Hz, 3H)
1-020 (* 3);
9.01 (d, J = 2.4 Hz, 1H), 8.61 (dd, J = 4.8, 1.2 Hz, 1H), 8.08 (ddd, J = 8.4, 2.4) 1.2 Hz, 1H), 8.01 (s, 1H), 7.44 (dd, J = 8.4, 4.8 Hz, 1H), 4.85 (d, J = 11.8 Hz, 1H), 4.78 (d, J = 11.8 Hz, 1H), 4.00-3.75 (m, 2H), 2.35 (s, 3H), 2.03 (s.3H), 1.22 ( t, J = 7.2 Hz, 3H)
1-023;
(Isomer ratio 3) 8.93 (d, J = 2.7 Hz, 1H), 8.61 (dd, J = 4.8, 1.2 Hz, 1H), 8.51 (s, 1H), 8 .01 (ddd, J = 8.4, 2.7, 1.2 Hz, 1H), 7.41 (dd, J = 8.4, 4.8 Hz, 1H), 4.10-3.35 (m , 3H), 2.80-2.65 (m, 2H), 2.11 (s, 3H), 1.45-1.10 (m, 9H)
(Isomer ratio 2) 9.01 (d, J = 2.7 Hz, 1H), 8.61 (dd, J = 4.8, 1.2 Hz, 1H), 8.15 (s, 1H), 8 .01 (ddd, J = 8.4, 2.7, 1.2 Hz, 1H), 7.42 (dd, J = 8.4, 4.8 Hz, 1H), 4.10-3.35 (m , 3H), 2.49 (q, J = 7.2 Hz, 2H), 2.11 (s, 3H), 1.45 to 1.10 (m, 9H)
1-024;
(Isomer ratio 27) 9.05-9.00 (m, 1H), 8.75-8.65 (m, 1H), 8.15 (s, 1H), 8.05-7.95 (m , 1H), 7.50-7.40 (m, 1H), 4.00-3.75 (m, 2H), 3.00-2.60 (m, 4H), 2.20-2.00 (M, 6H), 1.30-1.15 (m, 3H)
(Isomer ratio 25) 9.05-9.00 (m, 1H), 8.75-8.65 (m, 1H), 8.25 (s, 1H), 8.05-7.95 (m , 1H), 7.50-7.40 (m, 1H), 4.00-3.75 (m, 2H), 3.00-2.60 (m, 4H), 2.20-2.00 (M, 6H), 1.30-1.15 (m, 3H)
1-029;
(Isomer ratio 85) 8.89 (d, J = 2.7 Hz, 1H), 8.59 (dd, J = 4.8, 1.2 Hz, 1H), 8.03 (s, 1H), 8 .00 (ddd, J = 8.1, 2.7, 1.2 Hz, 1H), 7.43 (dd, J = 8.1, 4.8 Hz, 1H), 4.09 (q, J = 7 .2 Hz, 1 H), 3.75 (s, 3 H), 3.32 (s, 3 H), 1.90 (s, 3 H), 1.48 (d, J = 7.2 Hz, 3 H)
(Isomer ratio 15) 8.89 (d, J = 2.7 Hz, 1H), 8.59 (dd, J = 4.8, 1.2 Hz, 1H), 8.13 (s, 1H), 8 .00 (ddd, J = 8.1, 2.7, 1.2 Hz, 1H), 7.43 (dd, J = 8.1, 4.8 Hz, 1H), 4.38-4.27 (m , 1H), 3.97 (brs, 3H), 3.50 (brs, 3H), 2.20 (brs, 3H), 1.63-1.55 (m, 3H)
1-030;
(Isomer ratio 5) 8.99-8.89 (m, 1H), 8.64-8.54 (m, 1H), 8.06-7.95 (m, 1H), 7.99 (s , 1H), 7.48-7.36 (m, 1H), 4.22-4.00 (m, 1H), 3.76 (s, 3H), 3.32 (s, 3H), 57 (s, 3H), 1.52 (d, J = 7.5 Hz, 3H)
(Isomer ratio 4) 8.99-8.89 (m, 1H), 8.64-8.54 (m, 1H), 8.18 (s, 1H), 8.06-7.95 (m , 1H), 7.48-7.36 (m, 1H), 4.22-4.00 (m, 1H), 3.73 (s, 3H), 3.32 (s, 3H), 59 (s, 3H), 1.49 (d, J = 7.5 Hz, 3H)
(Isomer ratio 1) 8.99-8.89 (m, 1H), 8.64-8.54 (m, 1H), 8.11 (s, 1H), 8.06-7.95 (m , 1H), 7.48-7.36 (m, 1H), 4.22-4.00 (m, 1H), 3.84 (brs, 3H), 3.50 (brs, 3H), 65 (brs, 3H), 1.73-1.60 (m, 3H)
1-031;
(Isomer ratio 9) 8.95 (d, J = 2.7 Hz, 1H), 8.58 (d, J = 4.8 Hz, 1H), 8.11 (s, 1H), 7.9-7 .93 (m, 1H), 7.41 (dd, J = 8.1, 4.8 Hz, 1H), 4.64 (q, J = 7.2 Hz, 1H), 3.76 (s, 3H) , 3.32 (s, 3H), 2.94 (s, 3H), 1.76 (d, J = 7.2 Hz, 3H)
(Isomer ratio 1) 8.95 (d, J = 2.7 Hz, 1H), 8.58 (d, J = 4.8 Hz, 1H), 8.09 (s, 1H), 7.9-7 .93 (m, 1H), 7.41 (dd, J = 8.1, 4.8 Hz, 1H), 4.91-4.81 (m, 1H), 4.09 (brs, 3H), 3 .51 (brs, 3H), 3.03 (brs, 3H), 1.82-1.74 (m, 3H)
1-033;
(Isomer ratio 5) 8.97 (d, J = 2.4 Hz, 1H), 8.60 (dd, J = 4.8, 1.2 Hz, 1H), 8.24 (s, 1H), 8 .00 (ddd, J = 8.4, 2.4, 1.2 Hz, 1H), 7.43 (dd, J = 8.4, 4.8 Hz, 1H), 4.60-4.40 (m , 2H), 3.83 (s, 3H), 2.71 (s, 3H), 2.29 (t, J = 2.4 Hz, 1H), 1.75-1.60 (m, 4H)
(Isomer ratio 1) 9.00 (d, J = 2.1 Hz, 1H), 8.60 (dd, J = 4.8, 1.2 Hz, 1H), 8.25 (s, 1H), 8 .06-8.00 (m, 1H), 7.43 (dd, J = 8.4, 4.8 Hz, 1H), 4.60-4.40 (m, 2H), 3.83 (s, 3H), 3.11 (s, 3H), 2.26 (t, J = 2.1 Hz, 1H), 1.75-1.60 (m, 4H)
1-034;
8.89 (d, J = 2.4 Hz, 1H), 8.59 (dd, J = 4.8, 1.2 Hz, 1H), 8.05-7.95 (m, 2H), 7.43 (Dd, J = 8.4, 4.8 Hz, 1H), 3.93 (q, J = 7.2 Hz, 2H), 3.57 (s, 2H), 3.34 (s, 3H), 1 .94 (s, 3H), 1.02 (t, J = 7.2 Hz, 3H)
1-037;
(Isomer ratio 4) 8.96 (d, J = 2.7 Hz, 1H), 8.57 (dd, J = 4.8, 1.2 Hz, 1H), 8.24 (s, 1H), 7 .97 (ddd, J = 8.4, 2.7, 1.2 Hz, 1H), 7.40 (dd, J = 8.4, 4.8 Hz, 1H), 4.15-3.90 (m , 4H), 3.34 (s, 3H), 2.61 (s, 3H), 1.02 (t, J = 7.2 Hz, 3H)
(Isomer ratio 1) 8.96 (d, J = 2.7 Hz, 1H), 8.57 (dd, J = 4.8, 1.2 Hz, 1H), 8.24 (s, 1H), 7 .97 (ddd, J = 8.4, 2.7, 1.2 Hz, 1H), 7.40 (dd, J = 8.4, 4.8 Hz, 1H), 4.15-3.90 (m , 2H), 3.48 (q, J = 7.2 Hz, 2H), 3.34 (s, 3H), 2.61 (s, 3H), 1.20 (t, J = 7.2 Hz, 3H) )
1-042;
(Isomer ratio 3) 8.93 (d, J = 2.7 Hz, 1H), 8.63-8.57 (m, 1H), 8.07-7.93 (m, 1H), 7.96 (S, 1H), 7.44 (dd, J = 8.1, 4.8 Hz, 1H), 4.19-4.03 (m, 1H), 3.93-3.61 (m, 2H) 3.75 (s, 3H), 2.57 (s, 3H), 1.51 (d, J = 7.2 Hz, 3H), 1.30-1.15 (m, 3H)
(Isomer ratio 2) 8.97 (d, J = 2.7 Hz, 1H), 8.58-8.53 (m, 1H), 8.15 (s, 1H), 8.07-7.93 (M, 1H), 7.40 (dd, J = 8.1, 4.8 Hz, 1H), 4.19-4.03 (m, 1H), 3.93-3.61 (m, 2H) , 3.72 (s, 3H), 2.58 (s, 3H), 1.49 (d, J = 7.2 Hz, 3H), 1.30-1.15 (m, 3H)
1-043;
8.91 (d, J = 2.7 Hz, 1H), 8.58 (d, J = 4.8 Hz, 1H), 8.03-7.95 (m, 2H), 7.42 (dd, J = 8.7, 4.8 Hz, 1H), 5.09 (brs, 2H), 3.70 (brs, 3H), 3.54 (brs, 2H), 3.48 (s, 3H), 93 (brs, 3H)
1-044;
(Isomer ratio 85) 8.95 (d, J = 2.4 Hz, 1H), 8.58 (dd, J = 4.8, 1.2 Hz, 1H), 8.07 (s, 1H), 8 .02-7.94 (m, 1H), 7.41 (dd, J = 8.1, 4.8 Hz, 1H), 5.10 (brs, 2H), 4.47 (brs, 2H), 3 .82 (brs, 3H), 3.49 (s, 3H), 2.85 (s, 3H)
(Isomer ratio 15) 9.00 (d, J = 2.1 Hz, 1H), 8.58 (dd, J = 4.8, 1.2 Hz, 1H), 8.41 (s, 1H), 8 .09-7.94 (m, 1H), 7.41 (dd, J = 8.1, 4.8 Hz, 1H), 5.10 (brs, 2H), 4.47 (brs, 2H), 3 .82 (brs, 3H), 3.44 (s, 3H), 3.04 (s, 3H)
1-045;
8.90 (d, J = 2.4 Hz, 1H), 8.58 (dd, J = 4.8, 1.2 Hz, 1H), 8.07-7.93 (m, 2H), 7.43 (Dd, J = 8.4, 4.8 Hz, 1H), 5.14 (brs, 2H), 3.80-3.65 (m, 5H), 3.53 (brs, 2H), 1.93 (Brs, 3H), 1.35-1.20 (m, 3H)
1-046;
(Isomer ratio 92) 9.00-8.90 (m, 1H), 8.67-8.57 (m, 1H), 8.16 (s, 1H), 8.00 (ddd, J = 8 .4, 2.7, 1.2 Hz, 1H), 7.45 (dd, J = 8.4, 4.8 Hz, 1H), 4.63 (brs, 2H), 3.71 (brs, 3H) , 3.55 (brs, 2H), 1.93 (brs, 3H)
(Isomer ratio 8)
9.00-8.90 (m, 1H), 8.67-8.57 (m, 1H), 8.39 (s, 1H), 8.00 (ddd, J = 8.4, 2.7) , 1.2 Hz, 1H), 7.45 (dd, J = 8.4, 4.8 Hz, 1H), 4.68 (brs, 2H), 3.83 (s, 3H), 3.09 (s) , 2H), 2.00 (s, 3H)
1-047;
8.88 (d, J = 2.4 Hz, 1H), 8.59 (dd, J = 4.8, 1.2 Hz, 1H), 8.03 (s, 1H), 7.97 (ddd, J = 8.4, 2.4, 1.2 Hz, 1H), 7.42 (dd, J = 8.4, 4.8 Hz, 1H), 3.69 (d, J = 7.2 Hz, 2H), 3.59 (s, 2H), 3.34 (s, 3H), 1.95 (s, 3H), 0.95-0.80 (m, 1H), 0.40-0.25 (m, 2H), 0.15-0.05 (m, 2H)
1-048;
8.89 (d, J = 2.4 Hz, 1H), 8.58 (dd, J = 4.8 Hz, 1.2 Hz, 1H), 8.03 (s, 1H), 7.98 (ddd, J = 8.4, 2.4, 1.2 Hz, 1H), 7.42 (dd, J = 8.4, 4.8 Hz, 1H), 4.02 (t, J = 4.8 Hz, 2H), 3.58 (s, 2H), 3.40-3.30 (m, 2H), 3.34 (s, 3H), 3.14 (s, 3H), 1.94 (s, 3H)
1-050;
8.91 (d, J = 2.4 Hz, 1H), 8.58 (dd, J = 4.8, 1.2 Hz, 1H), 8.11 (s, 1H), 7.99 (ddd, J = 8.4, 2.4, 1.2 Hz, 1H), 7.41 (dd, J = 8.4, 4.8 Hz, 1H), 4.96 (s, 2H), 3.55 (s, 2H), 3.36 (s, 3H), 1.94 (s, 3H), 1.90 (s, 3H)
1-051;
8.89 (d, J = 2.7 Hz, 1H), 8.58 (dd, J = 4.8, 1.2 Hz, 1H), 8.05-7.95 (m, 2H), 7.43 (Dd, J = 8.4, 4.8 Hz, 1H), 4.03 (t, J = 7.2 Hz, 2H), 3.57 (s, 2H), 3.34 (s, 3H), 2 .47 (t, J = 7.2 Hz, 2H), 1.99 (s, 3H), 1.98 (s, 3H)
1-053;
8.97 (d, J = 2.4 Hz, 1H), 8.58 (dd, J = 4.8, 1.5 Hz, 1H), 8.25 (s, 1H), 8.00 (ddd, J = 8.4, 2.4, 1.5 Hz, 1H), 7.41 (dd, J = 8.4, 4.8 Hz, 1H), 5.05 to 4.95 (m, 2H), 4. 15-4.00 (m, 2H), 3.35 (s, 3H), 3.11 (s, 3H), 2.67 (s, 3H)
1-054;
(Isomer ratio 3) 8.85 (d, J = 2.4 Hz, 1H), 8.65-8.57 (m, 1H), 8.04-7.90 (m, 1H), 7.83 (S, 1H), 7.43 (dd, J = 8.1, 4.8 Hz, 1H), 4.04 (s, 3H), 3.33 (s, 3H), 2.26 (s, 3H) )
(Isomer ratio 2) 8.91 (d, J = 2.1 Hz, 1H), 8.65-8.57 (m, 1H), 8.04-7.90 (m, 1H), 7.95 (S, 1H), 7.43 (dd, J = 8.1, 4.8 Hz, 1H), 3.82 (s, 3H), 3.32 (s, 3H), 2.36 (s, 3H) )
1-055;
(Isomer ratio 50) 8.95 (d, J = 2.4 Hz, 1H), 8.70-8.55 (m, 1H), 8.13 (s, 1H), 8.05-7.95 (M, 1H), 7.41 (dd, J = 8.4, 4.8 Hz, 1H), 5.00 (s, 2H), 4.54 (s, 2H), 3.40-3.30. (M, 3H), 3.11 (s, 3H), 2.97 (s, 3H)
(Isomer ratio 7) 9.00 (d, J = 3.0 Hz, 1H), 8.70-8.55 (m, 1H), 8.46 (s, 1H), 8.05-7.95 (M, 1H), 7.41 (dd, J = 8.4, 4.8 Hz, 1H), 5.02 (s, 2H), 4.54 (s, 2H), 3.40-3.30. (M, 3H), 3.28 (s, 3H), 3.05 (s, 3H)
1-056;
8.93 (d, J = 2.7 Hz, 1H), 8.63 (dd, J = 4.8, 1.2 Hz, 1H), 8.20 (s, 1H), 8.01 (ddd, J = 8.1, 2.7, 1.2 Hz, 1H), 7.46 (dd, J = 8.1, 4.8 Hz, 1H), 4.75 (d, J = 17.4 Hz, 1H), 4.52 (d, J = 17.4 Hz, 1H), 4.12 (q, J = 7.2 Hz, 1H), 3.76 (s, 3H), 1.92 (s, 3H), 52 (d, J = 7.2 Hz, 3H)
1-056 (* 3);
(Isomer ratio 81) 8.91 (d, J = 2.4 Hz, 1H), 8.63 (dd, J = 4.8, 1.2 Hz, 1H), 8.36 (brs, 1H), 8 .00 (ddd, J = 8.1, 2.4, 1.2 Hz, 1H), 7.46 (dd, J = 8.1, 4.8 Hz, 1H), 4.95-4.32 (m , 2H), 3.88 (brs, 3H), 4.05-3.30 (m, 1H), 1.91 (brs, 3H), 1.41 (d, J = 7.2 Hz, 3H)
(Isomer ratio 19) 8.97 (d, J = 2.4 Hz, 1H), 8.67-8.59 (m, 1H), 8.21 (brs, 1H), 8.06-7.96 (M, 1H), 7.50-7.40 (m, 1H), 4.95-4.32 (m, 2H), 4.03 (brs, 3H), 4.05-3.30 (m , 1H), 2.18 (brs, 3H), 1.70-1.50 (m, 3H)
1-057 (* 3);
9.44 (brs, 1H), 8.98 (d, J = 2.4 Hz, 1H), 8.71 (s, 1H), 8.55 (dd, J = 4.8, 1.2 Hz, 1H) ), 7.99 (ddd, J = 8.1, 2.4, 1.2 Hz, 1H), 7.39 (dd, J = 8.1, 4.8 Hz, 1H), 4.17-4. 01 (m, 1H), 4.09 (s, 3H), 2.10 (s, 3H), 1.52 (d, J = 7.2 Hz, 3H)
1-058;
8.98-8.91 (m, 1H), 8.65-8.57 (m, 1H), 8.08 (s, 1H), 8.07-8.00 (m, 1H), 7. 44 (dd, J = 8.4, 4.8 Hz, 1H), 4.88 (brs, 2H), 3.70 (s, 3H), 3.53 (s, 2H), 2.26 (s, 3H), 1.93 (s, 3H)
1-059;
8.89 (d, J = 2.4 Hz, 1H), 8.59 (dd, J = 4.8, 1.2 Hz, 1H), 8.00 (ddd, J = 8.1, 2.4, 1.2 Hz, 1 H), 7.94 (s, 1 H), 7.43 (dd, J = 8.1, 4.8 Hz, 1 H), 6.00-5.81 (m, 1 H), 5. 30-5.16 (m, 2H), 4.41-4.28 (m, 2H), 3.69 (s, 3H), 3.54 (s, 2H), 1.92 (s, 3H)
1-060;
8.90 (d, J = 2.7 Hz, 1H), 8.63 (dd, J = 4.8, 1.2 Hz, 1H), 8.05-7.95 (m, 1H), 7.96 (S, 1H), 7.45 (dd, J = 8.4, 4.8 Hz, 1H), 4.42 (sep, J = 6.3 Hz, 1H), 3.38 (s, 3H), 1 .15 (d, J = 6.3 Hz, 6H)
1-065;
8.92 (d, J = 2.4 Hz, 1H), 8.60 (dd, J = 4.8, 1.2 Hz, 1H), 8.05-7.95 (m, 2H), 7.44 (Dd, J = 8.4, 4.8 Hz, 1H), 3.69 (s, 3H), 3.63 (d, J = 6.6 Hz, 2H), 3.53 (s, 2H), 1 .93 (s, 3H), 1.10-1.00 (m, 1H), 0.60-0.45 (m, 2H), 0.30-0.20 (m, 2H)
1-066;
(Isomer ratio 87) 8.94 (d, J = 2.1 Hz, 1H), 8.65-8.55 (m, 1H), 8.10-7.95 (m, 1H), 7.89 (S, 1H), 7.44 (dd, J = 8.4, 4.8 Hz, 1H), 6.20-6.00 (m, 1H), 4.00-3.25 (m, 8H) , 2.20-1.85 (m, 3H), 1.40-1.20 (m, 3H)
(Isomer ratio 13) 8.94 (d, J = 2.1 Hz, 1H), 8.65-8.55 (m, 1H), 8.10-7.95 (m, 1H), 7.89 (S, 1H), 7.44 (dd, J = 8.4, 4.8 Hz, 1H), 5.80-5.60 (m, 1H), 4.00-3.25 (m, 8H) , 2.20-1.85 (m, 3H), 1.40-1.20 (m, 3H)
1-067;
8.75-8.65 (m, 1H), 8.60-8.50 (m, 1H), 7.90-7.70 (m, 1H), 7.50-7.30 (m, 7H) ), 5.00-4.80 (m, 2H), 3.70-3.55 (m, 5H), 1.95-1.85 (m, 3H)
1-068;
(Isomer ratio 5) 8.94 (d, J = 2.7 Hz, 1H), 8.60 (dd, J = 4.8, 1.2 Hz, 1H), 8.05-7.95 (m, 2H), 7.42 (dd, J = 8.4, 4.8 Hz, 1H), 3.99 (s, 3H), 3.85 (s, 3H), 3.64 (s, 2H), 2 .14 (s, 3H)
(Isomer ratio 1) 9.00-8.90 (m, 1H), 8.60-8.50 (m, 1H), 8.05-7.95 (m, 2H), 7.40-7 .35 (m, 1H), 3.99 (s, 3H), 3.85 (s, 3H), 3.64 (s, 2H), 2.14 (s, 3H)
1-069;
8.74 (d, J = 2.4 Hz, 1H), 8.55 (dd, J = 4.8, 1.2 Hz, 1H), 7.99 (ddd, J = 8.4, 2.4) 1.2 Hz, 1H), 7.63 (s, 1H), 7.50-7.20 (m, 5H), 5.10 (s, 2H), 3.69 (s, 3H), 3.57 (S, 2H), 1.92 (s, 3H)
1-070;
8.77 (d, J = 2.7 Hz, 1H), 8.55 (dd, J = 4.8, 1.2 Hz, 1H), 7.90 (ddd, J = 8.1, 2.7, 1.2 Hz, 1H), 7.59 (s, 1H), 7.39 (dd, J = 8.1, 4.8 Hz, 1H), 7.35-7.15 (m, 4H), 4. 89 (brs, 2H), 3.69 (s, 3H), 3.57 (s, 2H), 1.93 (s, 3H)
1-071;
8.77 (d, J = 2.7 Hz, 1H), 8.56 (dd, J = 4.8, 1.2 Hz, 1H), 7.87 (ddd, J = 8.4, 2.7, 1.2 Hz, 1H), 7.56 (s, 1H), 7.50-7.20 (m, 5H), 4.88 (brs, 2H), 3.68 (s, 3H), 3.56 (S, 2H), 1.90 (s, 3H)
1-073;
8.90 (d, J = 2.7 Hz, 1H), 8.61 (dd, J = 4.8, 1.2 Hz, 1H), 8.10-7.90 (m, 2H), 7.44 (Dd, J = 8.4, 4.8 Hz, 1H), 5.80-5.60 (brs, 2H), 3.90-3.60 (brs, 3H), 3.57 (s, 2H) , 2.11 (s, 3H), 2.05-1.85 (brs, 3H)
1-074;
(Isomer ratio 5) 8.97 (d, J = 2.7 Hz, 1H), 8.63 (dd, J = 4.8, 1.2 Hz, 1H), 8.17 (s, 1H), 8 .00 (ddd, J = 8.1, 2.7, 1.2 Hz, 1H), 7.44 (dd, J = 8.1, 4.8 Hz, 1H), 5.90-5.70 (m , 1H), 4.20-3.40 (m, 5H), 2.20-1.85 (m, 3H), 1.35-1.10 (m, 3H)
(Isomer ratio 1) 9.01 (d, J = 2.7 Hz, 1H), 8.84 (s, 1H), 8.54 (dd, J = 4.8, 1.2 Hz, 1H), 8 .00 (ddd, J = 8.1, 2.7, 1.2 Hz, 1H), 7.44 (dd, J = 8.1, 4.8 Hz, 1H), 5.90-5.70 (m , 1H), 4.20-3.40 (m, 5H), 2.20-1.85 (m, 3H), 1.35-1.10 (m, 3H)
1-075;
(Isomer ratio 1) 9.05-8.90 (m, 1H), 8.65-8.50 (m, 1H), 8.05-7.90 (m, 2H), 7.41 (dd , J = 8.4, 4.8 Hz, 1H), 6.10-5.90 (m, 1H), 4.20-3.90 (m, 2H), 3.79 (s, 3H), 3 .60-3.45 (m, 3H), 2.67 (s, 3H), 1.40-1.20 (m, 3H)
(Isomer ratio 1) 9.05-8.90 (m, 1H), 8.65-8.50 (m, 1H), 8.05-7.90 (m, 2H), 7.41 (dd , J = 8.4, 4.8 Hz, 1H), 6.10-5.90 (m, 1H), 4.20-3.90 (m, 2H), 3.79 (s, 3H), 3 .60-3.45 (m, 3H), 2.44 (s, 3H), 1.40-1.20 (m, 3H)
1-077;
8.91 (d, J = 2.7 Hz, 1H), 8.59 (d, J = 4.8 Hz, 1H), 8.03 (s, 1H), 8.02-7.98 (m, 1H) ), 7.43 (dd, J = 8.4, 4.8 Hz, 1H), 5.20 (d, J = 9.6 Hz, 1H), 4.97 (d, J = 9.6 Hz, 1H) 4.20-4.00 (m, 1H), 3.76 (s, 3H), 3.49 (s, 3H), 1.94 (s, 3H), 1.52 (d, J = 7) .2Hz, 3H)
1-077 (* 3);
(Isomer ratio 5) 8.89 (d, J = 2.7 Hz, 1H), 8.65-8.55 (m, 1H), 8.30-7.95 (m, 2H), 7.44 (Dd, J = 8.4, 4.8 Hz, 1H), 5.50-4.70 (m, 2H), 3.92 (brs, 3H), 3.80-3.60 (m, 1H) 3.46 (s, 3H), 1.90 (brs, 3H), 1.50-1.30 (m, 3H)
(Isomer ratio 1) 8.94 (d, J = 2.7 Hz, 1H), 8.65-8.55 (m, 1H), 8.30-7.95 (m, 2H), 7.42 (Dd, J = 8.4, 4.8 Hz, 1H), 5.50-4.70 (m, 2H), 3.95 (s, 3H), 3.55 to 3.45 (m, 1H) , 3.39 (s, 3H), 1.90 (brs, 3H), 1.50-1.30 (m, 3H)
1-079;
8.96 (d, J = 2.7 Hz, 1H), 8.63 (dd, J = 4.8, 1.2 Hz, 1H), 8.14 (s, 1H), 8.02 (ddd, J = 8.4, 2.7, 1.2 Hz, 1H), 7.46 (dd, J = 8.4, 4.8 Hz, 1H), 5.85-5.60 (m, 1H), 4. 20-3.60 (m, 4H), 1.94 (brs, 3H), 1.65 to 1.45 (m, 3H), 1.13 (d, J = 6.0 Hz, 3H)
1-080;
(Isomer ratio 1) 9.00-8.80 (m, 1H), 8.70-8.55 (m, 1H), 8.10-7.95 (m, 2H), 7.55-7 .40 (m, 1H), 3.87 (s, 3H), 3.30 (s, 3H), 2.90-2.50 (m, 4H), 2.05 (s, 3H)
(Isomer ratio 1) 9.00-8.80 (m, 1H), 8.70-8.55 (m, 1H), 8.10-7.95 (m, 2H), 7.55-7 .40 (m, 1H), 3.69 (brs, 3H), 3.32 (brs, 3H), 2.90-2.50 (m, 4H), 2.12 (brs, 3H)
1-081;
8.82 (d, J = 2.4 Hz, 1H), 8.58 (dd, J = 4.8, 1.2 Hz, 1H), 7.95 (ddd, J = 8.4, 2.4) 1.2 Hz, 1H), 7.85 (s, 1H), 7.45-7.30 (m, 6H), 5.45-5.25 (m, 1H), 5.20-5.05 ( m, 1H), 4.75 (s, 2H), 4.10-4.00 (m, 1H), 3.75 (s, 3H), 1.94 (brs, 3H), 1.52 (d , J = 7.2Hz, 3H)
1-082;
(Isomer ratio 3) 9.05-8.95 (m, 1H), 8.70-8.55 (m, 1H), 8.21 (s, 1H), 8.10-7.95 (m , 1H), 7.50-7.35 (m, 1H), 4.90-4.45 (m, 2H), 4.30-4.10 (m, 1H), 3.79 (s, 3H) ), 2.56 (s, 3H), 1.65-1.50 (m, 3H)
(Isomer ratio 2) 9.05-8.95 (m, 1H), 8.70-8.55 (m, 1H), 8.35 (s, 1H), 8.10-7.95 (m , 1H), 7.50-7.35 (m, 1H), 4.90-4.45 (m, 2H), 4.30-4.10 (m, 1H), 3.78 (s, 3H) ), 2.60 (s, 3H), 1.65-1.50 (m, 3H)
1-084;
8.96 (d, J = 2.7 Hz, 1H), 8.70-8.55 (m, 1H), 8.09 (s, 1H), 8.05-7.95 (m, 1H), 7.43 (dd, J = 8.4, 4.8 Hz, 1H), 5.68 (brs, 2H), 4.47 (brs, 2H), 3.84 (brs, 3H), 2.89 ( brs, 3H), 2.10 (s, 3H)
1-085;
(Isomer ratio 4) 9.00-8.90 (m, 1H), 8.65-8.50 (m, 1H), 8.10-7.95 (m, 2H), 7.42 (dd , J = 8.4, 4.8 Hz, 1H), 4.35-4.15 (m, 3H), 3.97 (s, 3H), 3.80-3.60 (m, 1H), 2 .19 (s, 3H), 1.55-1.50 (m, 3H), 1.35-1.25 (m, 3H), 1.13 (d, J = 6.0 Hz, 3H)
(Isomer ratio 1) 9.00-8.90 (m, 1H), 8.65-8.50 (m, 1H), 8.10-7.95 (m, 2H), 7.42 (dd , J = 8.4, 4.8 Hz, 1H), 4.35-4.15 (m, 3H), 3.92 (s, 3H), 3.80-3.60 (m, 1H), 2 .15 (s, 3H), 1.55-1.50 (m, 3H), 1.35-1.25 (m, 3H), 1.13 (d, J = 6.0 Hz, 3H)
1-086;
8.88 (d, J = 2.4 Hz, 1H), 8.59 (dd, J = 4.8, 1.2 Hz, 1H), 8.05-7.95 (m, 2H), 7.43 (Dd, J = 8.4, 4.8 Hz, 1H), 5.90-5.50 (m, 2H), 4.25-3.70 (m, 4H), 1.95 (brs, 3H) , 1.53 (d, J = 7.2 Hz, 3H), 1.21 (s, 9H)
1-087;
8.90 (d, J = 2.4 Hz, 1H), 8.60 (dd, J = 4.8, 1.2 Hz, 1H), 8.10-7.95 (m, 2H), 7.43 (Dd, J = 8.4, 4.8 Hz, 1H), 5.80-5.60 (m, 2H), 4.12 (q, J = 7.2 Hz, 1H), 3.77 (brs, 3H), 2.10 (s, 3H), 1.93 (brs, 3H), 1.53 (d, J = 7.2 Hz, 3H)
1-088;
(Isomer ratio 20) 9.00-8.85 (m, 1H), 8.65-8.50 (m, 1H), 8.09 (s, 1H), 8.05-7.90 (m , 1H), 7.50-7.35 (m, 1H), 5.80-5.35 (m, 2H), 4.67 (q, J = 7.2 Hz, 1H), 3.81 (s) , 3H), 2.92 (s, 3H), 2.10 (s, 3H), 1.77 (d, J = 7.2 Hz, 3H)
(Isomer ratio 13) 9.00-8.85 (m, 1H), 8.65-8.50 (m, 1H), 8.12 (s, 1H), 8.05-7.90 (m , 1H), 7.50-7.35 (m, 1H), 5.60-4.90 (m, 2H), 4.76 (q, J = 7.2 Hz, 1H), 3.98 (s) , 3H), 2.95 (s, 3H), 2.10 (s, 3H), 1.76 (d, J = 7.2 Hz, 3H)
1-089;
8.89 (d, J = 2.7 Hz, 1H), 8.56 (d, J = 4.8, 1.2 Hz, 1H), 8.18 (s, 1H), 8.01 (ddd, J = 8.4, 2.7, 1.2 Hz, 1H), 7.41 (dd, J = 8.4, 4.8 Hz, 1H), 5.40-4.95 (m, 2H), 4. 09 (q, J = 7.2 Hz, 1H), 3.90-3.80 (m, 2H), 3.75 (s, 3H), 3.65-3.55 (m, 2H), 3. 39 (s, 3H), 1.93 (s, 3H), 1.51 (d, J = 7.2 Hz, 3H)
1-090;
(Isomer ratio 4) 8.94 (d, J = 2.4 Hz, 1H), 8.59 (dd, J = 4.8, 1.2 Hz, 1H), 8.10-7.95 (m, 2H), 7.43 (dd, J = 8.4, 4.8 Hz, 1H), 5.40-4.80 (m, 2H), 4.30-3.90 (m, 1H), 3. 77 (s, 3H), 3.47 (s, 3H), 2.57 (s, 3H), 1.56 (d, J = 7.2 Hz, 3H)
(Isomer ratio 1) 8.96 (d, J = 2.4 Hz, 1H), 8.56 (dd, J = 4.8, 1.2 Hz, 1H), 8.16 (s, 1H), 8 10-7.95 (m, 1H), 7.60-7.35 (m, 1H), 5.40-4.80 (m, 2H), 4.30-3.90 (m, 4H) , 3.50 (s, 3H), 2.57 (s, 3H), 1.52 (d, J = 7.2 Hz, 3H)
1-090 (* 3);
(Isomer ratio 6) 9.00-8.85 (m, 1H), 8.60-8.55 (m, 1H), 8.50-7.95 (m, 2H), 7.50-7 .35 (m, 1H), 5.35-4.60 (m, 2H), 3.91 (s, 3H), 3.80-3.40 (m, 4H), 2.63 (brs, 3H) ), 1.60-1.30 (m, 3H)
(Isomer ratio 1) 9.00-8.85 (m, 1H), 8.60-8.55 (m, 1H), 8.50-7.95 (m, 2H), 7.50-7 .35 (m, 1H), 5.35-4.60 (m, 2H), 4.01 (s, 3H), 3.80-3.30 (m, 4H), 2.55 (brs, 3H) ), 1.60-1.30 (m, 3H)
1-091;
8.96 (d, J = 2.4 Hz, 1H), 8.57 (dd, J = 4.8, 1.2 Hz, 1H), 8.10 (s, 1H), 8.05-7.90 (M, 1H), 7.41 (dd, J = 8.4, 4.8 Hz, 1H), 5.40-5.20 (m, 1H), 4.95-4.75 (m, 1H) 4.69 (q, J = 7.2 Hz, 1H), 3.81 (s, 3H), 3.49 (s, 3H), 2.90 (s, 3H), 1.77 (d, J = 7.2Hz, 3H)
1-092;
(Isomer ratio 4) 8.86 (d, J = 2.7 Hz, 1H), 8.65-8.50 (m, 1H), 8.05-7.90 (m, 1H), 7.79 (S, 1H), 7.50-7.20 (m, 6H), 5.55-4.60 (m, 4H), 4.30-4.00 (m, 1H), 3.77 (s , 3H), 2.60 (s, 3H), 1.54 (d, J = 7.2 Hz, 3H)
(Isomer ratio 3) 8.90 (d, J = 2.7 Hz, 1H), 8.65-8.50 (m, 1H), 8.07 (s, 1H), 8.05-7.90 (M, 1H), 7.50-7.20 (m, 6H), 5.55-4.60 (m, 4H), 4.30-4.00 (m, 1H), 3.77 (s , 3H), 2.58 (s, 3H), 1.54 (d, J = 7.2 Hz, 3H)
1-093;
8.90 (d, J = 2.4 Hz, 1H), 8.56 (dd, J = 4.8, 1.2 Hz, 1H), 8.02 (s, 1H), 7.92 (ddd, J = 8.4, 2.4, 1.2 Hz, 1H), 7.45-7.25 (m, 6H), 5.60-5.45 (m, 1H), 5.10-4.85 ( m, 1H), 4.85-4.65 (m, 3H), 3.81 (s, 3H), 2.93 (s, 3H), 1.79 (d, J = 7.2 Hz, 3H)
1-094;
8.90 (d, J = 2.4 Hz, 1H), 8.58 (dd, J = 4.8, 1.2 Hz, 1H), 8.10-7.90 (m, 2H), 7.43 (Dd, J = 8.4, 4.8 Hz, 1H), 5.35-5.15 (m, 1H), 5.10-4.90 (m, 1H), 4.09 (q, J = 7.2 Hz, 1H), 3.85-3.65 (m, 5H), 1.93 (brs, 3H), 1.51 (d, J = 7.2 Hz, 3H), 1.05-0. 90 (m, 2H), 0.03 (s, 9H)
1-095;
8.90-8.80 (m, 1H), 8.60-8.50 (m, 1H), 8.15-7.90 (m, 4H), 7.65-7.30 (m, 4H) ), 6.10-5.60 (m, 2H), 4.25-4.00 (m, 1H), 3.77 (brs, 3H), 1.95 (brs, 3H), 1.55 ( d, J = 7.2 Hz, 3H)
1-096;
8.89 (d, J = 2.4 Hz, 1H), 8.59 (dd, J = 4.8, 1.2 Hz, 1H), 8.10-7.95 (m, 2H), 7.43 (Dd, J = 8.4, 4.8 Hz, 1H), 5.90-5.55 (m, 2H), 4.25-3.85 (m, 1H), 3.76 (s, 3H) , 2.34 (t, J = 7.2 Hz, 2H), 1.93 (brs, 3H), 1.75-1.60 (m, 2H), 1.53 (d, J = 7.2 Hz, 3H), 0.94 (t, J = 7.2 Hz, 3H)
1-098;
8.96 (d, J = 2.4 Hz, 1H), 8.58 (dd, J = 4.8, 1.2 Hz, 1H), 8.07 (s, 1H), 8.05-7.90 (M, 1H), 7.41 (dd, J = 8.4, 4.8 Hz, 1H), 5.45-5.25 (m, 1H), 5.05-4.80 (m, 1H) 4.68 (q, J = 7.2 Hz, 1H), 3.81 (s, 3H), 3.85-3.65 (m, 2H), 2.90 (s, 3H), 1.76. (D, J = 7.2 Hz, 3H), 1.24 (t, J = 7.2 Hz, 3H)
1-099;
8.93 (d, J = 2.7 Hz, 1H), 8.61 (dd, J = 4.8, 1.2 Hz, 1H), 8.16 (s, 1H), 8.01 (ddd, J = 8.4, 2.7, 1.2 Hz, 1H), 7.43 (dd, J = 8.4, 4.8 Hz, 1H), 4.11 (q, J = 7.2 Hz, 1H), 3.86 (s, 3H), 3.54 (s, 3H), 1.99 (s, 3H), 1.60-1.50 (m, 3H)
1-100;
8.90 (d, J = 2.7 Hz, 1H), 8.58 (dd, J = 4.8, 1.2 Hz, 1H), 8.17 (s, 1H), 7.98 (ddd, J = 8.4, 2.7, 1.2 Hz, 1H), 7.45-7.35 (m, 1H), 6.25-5.90 (m, 1H), 5.65-5.25 ( m, 1H), 4.60-4.05 (m, 3H), 3.76 (s, 3H), 1.97 (s, 3H), 1.52 (d, J = 7.2 Hz, 3H)
1-102;
8.93 (d, J = 2.7 Hz, 1H), 8.58 (dd, J = 4.8, 1.2 Hz, 1H), 8.05-7.95 (m, 1H), 8.03 (S, 1H), 7.42 (dd, J = 8.4, 4.8 Hz, 1H), 4.21 (q.J = 7.2 Hz, 1H), 3.97 (s, 3H), 3 .83 (s, 3H), 2.18 (s, 3H), 1.65 to 1.50 (m, 3H)
1-103;
8.97 (d, J = 2.4 Hz, 1H), 8.69 (s, 1H), 8.57 (brs, 1H), 8.54 (dd, J = 4.8, 1.2 Hz, 1H) ), 7.98 (ddd, J = 8.4, 2.4, 1.2 Hz, 1H), 7.38 (dd, J = 8.4, 4.8 Hz, 1H), 4.42 (q, J = 7.2 Hz, 1H), 4.09 (s, 3H), 2.65-2.50 (m, 2H), 1.62 (d, J = 7.2 Hz, 3H), 1.27 ( t, J = 7.2 Hz, 3H)
1-104;
(Isomer ratio 95) 8.92 (d, J = 2.7 Hz, 1H), 8.62 (dd, J = 4.8, 1.2 Hz, 1H), 8.17 (s, 1H), 8 .00 (ddd, J = 8.4, 2.7, 1.2 Hz, 1H), 7.44 (dd, J = 8.4, 4.8 Hz, 1H), 4.72 (d, J = 17 .2 Hz, 1H), 4.54 (d, J = 17.2 Hz, 1H), 4.23-3.98 (m, 1H), 3.75 (s, 3H), 2.41-2.25. (M, 2H), 1.51 (d, J = 7.5 Hz, 3H), 1.14 (t, J = 7.2 Hz, 3H)
(Isomer ratio 5) 8.97 (s, 1H), 8.92 (d, J = 2.7 Hz, 1H), 8.62 (dd, J = 4.8, 1.2 Hz, 1H), 8 .00 (ddd, J = 8.4, 2.7, 1.2 Hz, 1H), 7.44 (dd, J = 8.4, 4.8 Hz, 1H), 4.95-4.85 (m , 1H), 4.63-4.49 (m, 1H), 4.23-3.98 (m, 1H), 3.75 (s, 3H), 2.77-2.41 (m, 2H) ), 1.42 (d, J = 7.2 Hz, 3H), 1.14 (t, J = 7.2 Hz, 3H)
1-105 (* 3);
(Isomer ratio 2) 9.00-8.80 (m, 1H), 8.65-8.55 (m, 1H), 8.28 (brs, 1H), 8.05-7.95 (m , 1H), 7.55-7.35 (m, 1H), 6.00-5.55 (m, 2H), 4.00-3.60 (m, 7H), 1.92 (brs, 3H) ), 1.41 (d, J = 7.2 Hz, 3H)
(Isomer ratio 1) 9.00-8.80 (m, 1H), 8.65-8.55 (m, 1H), 8.09 (s, 1H), 8.05-7.95 (m , 1H), 7.55-7.35 (m, 1H), 6.00-5.35 (m, 2H), 4.00-3.60 (m, 7H), 2.15 (brs, 3H) ), 1.60-1.40 (brs, 3H)
1-112;
(Isomer ratio 50) 8.87 (d, J = 2.4 Hz, 1H), 8.58 (dd, J = 4.8, 1.2 Hz, 1H), 8.05-7.95 (m, 2H), 7.42 (dd, J = 8.4, 4.8 Hz, 1H), 5.85-5.60 (m, 2H), 4.25-3.60 (m, 4H), 3. 40-3.20 (m, 4H), 1.94 (brs, 3H), 1.62 (d, J = 7.2 Hz, 3H), 1.20-1.00 (m, 6H)
(Isomer ratio 6) 8.95 (d, J = 2.4 Hz, 1H), 8.60-8.50 (m, 1H), 8.24 (s, 1H), 8.05-7.95 (M, 1H),
7.45-7.35 (m, 1H), 5.85-5.60 (m, 2H), 4.25-3.60 (m, 4H), 3.40-3.20 (m, 4H) ), 1.94 (brs, 3H), 1.62 (d, J = 7.2 Hz, 3H), 1.20-1.00 (m, 6H)
1-113;
(Isomer ratio 83) 8.94 (d, J = 2.7 Hz, 1H), 8.65-8.55 (m, 1H), 8.10-8.00 (m, 1H), 7.91 (S, 1H), 7.50-7.40 (m, 1H), 6.15-5.95 (m, 1H), 4.10-3.90 (m, 1H), 3.75 (s , 3H), 3.53 (s, 3H), 1.86 (brs, 3H), 1.55-1.20 (m, 6H)
(Isomer ratio 10) 9.00-8.90 (m, 1H), 8.65-8.55 (m, 1H), 8.10-8.00 (m, 1H), 7.89 (s , 1H), 7.50-7.40 (m, 1H), 5.55-5.35 (m, 1H), 4.10-3.90 (m, 1H), 3.55 (s, 3H) ), 3.53 (s, 3H), 2.08 (brs, 3H), 1.55-1.20 (m, 6H)
1-114;
8.93 (d, J = 2.4 Hz, 1H), 8.60 (dd, J = 4.8, 1.2 Hz, 1H), 8.11 (s, 1H), 8.03 (ddd, J = 8.1, 2.4, 1.2 Hz, 1H), 7.43 (dd, J = 8.1, 4.8 Hz, 1H), 5.14-4.98 (m, 1H), 4. 70-4.60 (m, 1H), 4.10 (q, J = 7.2 Hz, 1H), 3.75 (s, 3H), 2.26 (s, 3H), 1.93 (s, 3H), 1.51 (d, J = 7.2 Hz, 3H)
1-115;
(Isomer ratio 83) 8.92 (d, J = 2.4 Hz, 1H), 8.60 (d, J = 4.5 Hz, 1H), 8.06-7.99 (m, 1H), 7 .86 (s, 1H), 7.44 (dd, J = 8.1, 4.5 Hz, 1H), 6.22-6.02 (m, 1H), 4.35-3.55 (m, 3H), 3.74 (s, 3H), 2.30-1.80 (m, 3H), 1.68-1.10 (m, 9H)
(Isomer ratio 17) 8.92 (d, J = 2.4 Hz, 1H), 8.60 (d, J = 4.5 Hz, 1H), 8.06-7.9 (m, 1H), 7 .86 (s, 1H), 7.44 (dd, J = 8.1, 4.5 Hz, 1H), 5.62-5.48 (m, 1H), 4.35-3.55 (m, 3H), 3.74 (s, 3H), 2.30-1.80 (m, 3H), 1.68-1.10 (m, 9H)
1-116 (* 3)
9.12 (brs, 1H), 8.99 (d, J = 2.4 Hz, 1H), 8.62 (s, 1H), 8.50 (dd, J = 4.8, 1.2 Hz, 1H) ), 7.98 (ddd, J = 8.4, 2.4, 1.2 Hz, 1H), 7.36 (dd, J = 8.4, 4.8 Hz, 1H), 4.08 (s, 3H), 4.05 (q, J = 7.2 Hz, 1H), 2.35 (s, 3H), 2.08 (s, 3H), 1.53 (d, J = 7.2 Hz, 3H)
1-118;
8.92 (d, J = 2.4 Hz, 1H), 8.60 (dd, J = 4.8, 1.2 Hz, 1H), 8.11 (s, 1H), 8.10-7.95 (M, 1H), 7.50-7.35 (m, 1H), 5.90-5.70 (m, 1H), 5.65-5.40 (m, 1H), 4.40-4 .20 (m, 3H), 3.75 (brs, 3H), 3.65-3.50 (m, 2H), 3.36 (s, 3H), 1.92 (brs, 3H), 1. 53 (d, J = 7.2 Hz, 3H)
1-119;
8.96 (d, J = 2.4 Hz, 1H), 8.59 (dd, J = 4.8, 1.2 Hz, 1H), 8.14 (s, 1H), 8.05-7.90 (M, 1H), 7.42 (dd, J = 8.4, 4.8 Hz, 1H), 6.00-5.75 (m, 1H), 5.65-5.35 (m, 1H) , 4.80-4.55 (m, 1H), 4.29 (t, J = 4.5 Hz, 2H), 3.81 (s, 3H), 3.60 (t, J = 4.5 Hz, 2H), 3.36 (s, 3H), 2.93 (s, 3H), 1.76 (d, J = 7.2 Hz, 3H)
1-120;
(Isomer ratio 87) 9.00-8.95 (m, 1H), 8.61-8.58 (m, 1H), 8.14 (s, 1H), 8.12-8.02 (m , 1H), 7.44 (dd, J = 8.1, 4.8 Hz, 1H), 6.53 (s, 1H), 3.61 (s, 3H), 3.41 (s, 3H), 3.15 (q, J = 7.2 Hz, 1H), 2.10 (s, 3H), 1.45 (d, J = 7.2 Hz, 3H)
(Isomer ratio 13) 9.00-8.95 (m, 1H), 8.61-8.58 (m, 1H), 8.14 (s, 1H), 8.12-8.02 (m , 1H), 7.44 (dd, J = 8.1, 4.8 Hz, 1H), 6.45 (s, 1H), 3.56 (s, 3H), 3.43 (s, 3H), 3.24 (q, J = 7.2 Hz, 1H), 2.25 (s, 3H), 1.38 (d, J = 7.2 Hz, 3H)
1-122;
(Isomer ratio 93) 8.98 (d, J = 2.7 Hz, 1H), 8.69 (s, 1H), 8.64 (brs, 1H), 8.55 (dd, J = 4.8) , 1.2 Hz, 1H), 7.98 (ddd, J = 8.4, 2.7, 1.2 Hz, 1H), 7.39 (dd, J = 8.4, 4.8 Hz, 1H), 4.07 (s, 3H), 3.82 (d, J = 10.8 Hz, 1H), 2.58-2.40 (m, 1H), 2.13 (s, 3H), 1.44 ( d, J = 6.6 Hz, 3H), 0.90 (d, J = 6.6 Hz, 3H)
(Isomer ratio 7) 9.51 (brs, 1H), 8.98 (d, J = 2.7 Hz, 1H), 8.71 (s, 1H), 8.55 (dd, J = 4.8) , 1.2 Hz, 1H), 7.98 (ddd, J = 8.4, 2.7, 1.2 Hz, 1H), 7.39 (dd, J = 8.4, 4.8 Hz, 1H), 4.08 (s, 3H), 3.40 (d, J = 10.5 Hz, 1H), 2.58-2.40 (m, 1H), 2.09 (s, 3H), 1.44 ( d, J = 6.6 Hz, 3H), 0.90 (d, J = 6.6 Hz, 3H)
1-128;
8.97 (d, J = 2.4 Hz, 1H), 8.57 (dd, J = 4.8, 1.2 Hz, 1H), 8.10-7.95 (m, 1H), 7.90 −7.80 (m, 1H), 7.42 (dd, J = 8.4, 4.8 Hz, 1H), 7.30-7.20 (m, 1H), 5.85-5.45 ( m, 2H), 4.00-3.80 (m, 7H), 2.25-1.80 (m, 3H), 1.60-1.50 (brs, 3H)
1-129;
8.98 (d, J = 2.7 Hz, 1H), 8.65-8.50 (m, 1H), 8.20-7.70 (m, 2H), 7.41 (dd, J = 8 .4, 4.8 Hz, 1H), 7.30-7.20 (m, 1H), 5.80-5.40 (m, 2H), 5.00-4.60 (m, 1H), 3 .81 (s, 3H), 3.80 (s, 3H), 3.25-2.60 (m, 3H), 1.76 (d, J = 7.2 Hz, 3H)
1-132;
(Isomer ratio 3) 8.91 (d, J = 2.4 Hz, 1H), 8.60 (dd, J = 4.8, 1.2 Hz, 1H), 8.09 (s, 1H), 8 .01 (ddd, J = 8.4, 2.4, 1.2 Hz, 1H), 7.43 (dd, J = 8.4, 4.8 Hz, 1H), 5.90-5.35 (m , 2H), 3.90-3.50 (m, 7H), 2.40-2.20 (m, 1H), 1.87 (brs, 3H), 1.14 (d, J = 6.0 Hz) , 6H)
(Isomer ratio 1) 9.00-8.85 (m, 1H), 8.65-8.50 (m, 1H), 8.12 (s, 1H), 8.05-7.90 (m , 1H), 7.43 (dd, J = 8.4, 4.8 Hz, 1H), 5.90-5.35 (m, 2H), 3.90-3.50 (m, 7H), 2 .40-2.20 (m, 1H), 1.87 (brs, 3H), 0.98 (d, J = 6.0 Hz, 6H)
1-142;
8.95-8.85 (m, 1H), 8.54 (dd, J = 4.8, 1.2 Hz, 1H), 8.05-7.95 (m, 1H), 7.95 (s) , 1H), 7.40 (dd, J = 8.4, 4.8 Hz, 1H), 5.70-5.50 (m, 2H), 4.30-3.90 (m, 1H), 3 .75 (brs, 3H), 2.45-2.20 (m, 5H), 2.10 (s, 3H), 1.55-1.45 (m, 3H), 1.20-1.05 (M, 3H)
1-143;
8.91 (d, J = 2.4 Hz, 1H), 8.53 (dd, J = 4.8, 1.2 Hz, 1H), 8.05-7.95 (m, 2H), 7.40 (Dd, J = 8.4, 4.8 Hz, 1H), 5.85-5.45 (m, 2H), 4.25-4.10 (m, 1H), 3.79 (s, 3H) , 3.75 (brs, 3H), 2.40-2.15 (m, 5H), 1.60-1.40 (m, 3H), 1.25-1.00 (m, 3H)
1-144;
(Isomer ratio 5) 8.88 (d, J = 2.4 Hz, 1H), 8.54 (dd, J = 4.8, 1.2 Hz, 1H), 8.20-7.95 (m, 2H), 7.40 (dd, J = 8.4, 4.8 Hz, 1H), 5.30-4.75 (m, 2H), 4.05-3.80 (m, 4H), 3. 47 (s, 3H), 2.31 (s, 3H), 1.81 (s, 3H), 1.38 (d, J = 7.2 Hz, 3H)
(Isomer ratio 1) 8.92 (d, J = 2.4 Hz, 1H), 8.50 (dd, J = 4.8, 1.2 Hz, 1H), 8.20-7.95 (m, 2H), 7.45-7.30 (m, 1H), 5.30-4.75 (m, 2H), 4.05-3.80 (m, 4H), 3.38 (s, 3H) , 2.27 (s, 3H), 2.16 (s, 3H), 1.58 (d, J = 7.2 Hz, 3H)
1-145;
8.90 (d, J = 2.7 Hz, 1H), 8.60-8.45 (m, 2H), 8.15-8.00 (m, 1H), 7.38 (dd, J = 8 .4, 4.8 Hz, 1H), 4.59 (q, J = 7.2 Hz, 1H), 4.47 (q, J = 7.2 Hz, 1H), 4.14 (s, 3H), 4 0.00 (s, 3H), 2.75-2.55 (m, 2H), 2.46 (s, 3H), 2.12 (s, 3H), 1.69 (d, J = 7.2 Hz) , 3H), 1.59 (d, J = 7.2 Hz, 3H), 1.28 (t, J = 7.2 Hz, 3H)
1-148;
(Isomer ratio 2) 8.89 (d, J = 2.7 Hz, 1H) 8.55 (dd, J = 4.8, 1.2 Hz, 1H), 8.05-7.95 (m, 1H) ), 7.85 (s, 1H), 7.45-7.35 (m, 1H), 4.20-4.00 (m, 1H), 3.78 (s, 3H), 3.29 ( s, 3H), 2.57 (s, 3H), 2.31 (s, 3H), 2.30-1.70 (m, 2H), 0.90 (t, J = 7.2 Hz, 3H)
(Isomer ratio 1) 8.96 (d, J = 2.7 Hz, 1H) 8.50 (dd, J = 4.8, 1.2 Hz, 1H), 8.08 (s, 1H), 8. 05-7.95 (m, 1H), 7.45-7.35 (m, 1H), 4.20-4.00 (m, 1H), 3.71 (s, 3H), 3.28 ( s, 3H), 2.49 (s, 3H), 2.33 (s, 3H), 2.30-1.70 (m, 2H), 1.03 (t, J = 7.2 Hz, 3H)
1-149;
(Isomer ratio 25) 8.95 (d, J = 2.7 Hz, 1H) 8.52 (dd, J = 4.8, 1.2 Hz, 1H), 8.02 (s, 1H), 8. 05-7.90 (m, 1H), 7.37 (dd, J = 8.4, 4.8 Hz, 1H), 4.57 (q, J = 5.1 Hz, 1H), 3.73 (s , 3H), 3.29 (s, 3H), 2.81 (s, 3H), 2.33 (s, 3H), 2.30-2.10 (m, 2H), 1.06 (t, J = 7.2Hz, 3H)
(Isomer ratio 3) 9.00-8.90 (m, 1H), 8.60-8.45 (m, 1H), 8.10-7.90 (m, 2H), 7.45-7 .30 (m, 1H), 4.80-4.50 (m, 1H), 4.07 (s, 3H), 3.50 (s, 3H), 3.01 (s, 3H), 2. 45-2.10 (m, 5H), 1.15-1.00 (m, 3H)
1-153;
8.81 (d, J = 2.7 Hz, 1H), 8.60-8.55 (m, 3H), 7.95-7.85 (m, 1H), 7.33 (s, 1H), 7.45-7.35 (m, 1H), 7.30-7.20 (m, 2H), 5.07 (d, J = 15.0 Hz, 1H), 4.79 (d, J = 15 .0 Hz, 1H), 4.19 (q, J = 7.2 Hz, 1H), 3.77 (s, 3H), 2.45-2.30 (m, 2H), 1.56 (d, J = 7.2 Hz, 3H), 1.16 (t, J = 7.5 Hz, 3H)
1-154;
(Isomer ratio 8) 9.02-8.96 (m, 1H), 8.57 (s, 1H), 8.56-8.46 (m, 1H), 8.30 (brs, 1H), 8.03-7.96 (m, 1H), 7.45-7.35 (m, 1H), 4.45-4.25 (m, 1H), 4.20-4.10 (m, 3H) ), 2.53 (s, 3H), 2.45-2.15 (m, 5H), 1.20-0.95 (m, 3H)
(Isomer ratio 7) 9.76 (brs, 1H), 9.02-8.96 (m, 1H), 8.57 (s, 1H), 8.56-8.46 (m, 1H), 8.03-7.96 (m, 1H), 7.45-7.35 (m, 1H), 4.45-4.25 (m, 1H), 4.20-4.10 (m, 3H) ), 2.68 (s, 3H), 2.45-2.15 (m, 5H), 1.20-0.95 (m, 3H)
1-155;
8.98 (d, J = 2.4 Hz, 1H), 8.53 (s, 1H), 8.51 (dd, J = 4.8, 1.2 Hz, 1H), 8.39 (brs, 1H) ), 8.00 (ddd, J = 8.1, 2.4, 1.2 Hz, 1H), 7.38 (dd, J = 8.1, 4.8 Hz, 1H), 4.89 (dd, J = 10.5, 4.8 Hz, 1H), 4.17 (s, 3H), 3.11 (s, 3H), 2.55-2.40 (m, 1H), 2.38 (s, 3H), 2.36-2.20 (m, 1H), 1.03 (t, J = 7.5 Hz, 3H)
1-156;
8.98 (d, J = 2.4 Hz, 1H), 8.60 (s, 1H), 8.49 (dd, J = 4.5, 1.2 Hz, 1H), 8.37 (brs, 1H) ), 7.98 (ddd, J = 8.1, 2.4, 1.2 Hz, 1H), 7.36 (dd, J = 8.1, 4.5 Hz, 1H), 4.48 (dd, J = 9.0, 6.6 Hz, 1H), 4.10-4.40 (m, 4H), 3.80 (dd, J = 9.0, 6.6 Hz, 1H), 3.37 (s) , 3H), 2.38 (s, 3H), 2.22 (s, 3H)
1-160;
8.89 (d, J = 2.4 Hz, 1H), 8.53 (dd, J = 4.8, 1.2 Hz, 1H), 8.00 (ddd, J = 8.4, 2.4) 1.2 Hz, 1H), 7.97 (s, 1H), 7.39 (dd, J = 8.4, 4.8 Hz, 1H), 5.80-5.20 (m, 2H), 4. 00-3.60 (m, 4H), 2.45-2.25 (m, 3H), 2.20-1.95 (m, 5H), 1.80 (brs, 3H), 1.03 ( t, J = 7.5Hz, 3H)
1-162;
8.97 (d, J = 2.7 Hz, 1H), 8.54 (s, 1H), 8.49 (dd, J = 4.8, 1.8 Hz, 1H), 8.29 (brs, 1H) ), 7.98 (ddd, J = 8.7, 2.7, 1.8 Hz, 1H), 7.36 (dd, J = 8.7, 4.8 Hz, 1H), 5.23 (dd, J = 8.1, 5.4 Hz, 1H), 4.42 (dd, J = 10.2, 8.1 Hz, 1H), 4.17 (s, 3H), 3.96 (dd, J = 10 .2, 5.4 Hz, 1H), 3.42 (s, 3H), 3.13 (s, 3H), 2.37 (s, 3H)
1-163;
8.98 (d, J = 2.4 Hz, 1H), 8.43 (dd, J = 4.8, 0.9 Hz, 1H), 8.03-7.96 (m, 1H), 7.92 (S, 1H), 7.39 (dd, J = 8.1, 4.8 Hz, 1H), 5.18 (d, J = 10.2 Hz, 1H), 5.00 (d, J = 10. 2Hz, 1H), 4.12 (q, J = 6.9 Hz, 2H), 3.85-3.75 (m, 1H), 3.74 (s, 3H), 2.34 (s, 3H) , 1.84 (s, 3H), 1.47 (d, J = 7.5 Hz, 3H), 1.25 (t, J = 6.9 Hz, 3H)
1-164;
8.89 (d, J = 2.1 Hz, 1H), 8.52 (dd, J = 4.8, 1.2 Hz, 1H), 8.02-7.90 (m, 2H), 7.38 (dd, J = 8.1, 4.8 Hz, 1H), 5.75-5.40 (m, 2H), 4.20-3.60 (m, 9H), 3.36 (s, 3H) 3.32 (s, 3H), 2.04 (s, 3H)
1-165;
9.00-8.90 (m, 1H), 8.60-8.50 (m, 1H), 8.10-7.85 (m, 2H), 7.45-7.35 (m, 1H) ), 5.80-5.40 (m, 2H), 4.60-4.30 (m, 1H), 4.10-3.70 (m, 8H), 3.50-3.30 (m) , 3H), 2.80-2.50 (m, 3H), 2.40-2.20 (m, 3H)
1-166;
8.94 (d, J = 2.1 Hz, 1H), 8.53 (dd, J = 4.8, 1.5 Hz, 1H), 8.02-7.90 (m, 2H), 7.38 (dd, J = 8.1, 4.8 Hz, 1H), 5.80-5.40 (m, 2H), 5.00-4.80 (m, 1H), 4.28 (dd, J = 10.2, 9.3 Hz, 1H), 3.89 (dd, J = 10.2, 3.6 Hz, 1H), 3.80-3.70 (m, 6H), 3.41 (s, 3H) ), 3.03 (s, 3H), 2.32 (s, 3H)
1-167;
(Isomer ratio 3) 8.90 (d, J = 1.8 Hz, 1H), 8.55 (dd, J = 4.8, 1.2 Hz, 1H), 8.10-7.80 (m, 2H), 7.45-7.35 (m, 1H), 5.80-5.40 (m, 2H), 4.20-3.70 (m, 7H), 2.70-2.40 ( m, 3H), 2.40-2.10 (m, 4H), 2.00-1.70 (m, 1H), 1.20-0.80 (m, 3H)
(Isomer ratio 2) 8.94 (d, J = 2.1 Hz, 1H), 8.51 (dd, J = 4.5, 1.5 Hz, 1H), 8.10-7.80 (m, 2H), 7.45-7.35 (m, 1H), 5.80-5.40 (m, 2H), 4.20-3.70 (m, 7H), 2.70-2.40 ( m, 3H), 2.40-2.10 (m, 4H), 2.00-1.70 (m, 1H), 1.20-0.80 (m, 3H)
1-168;
8.94 (d, J = 2.4 Hz, 1H), 8.53 (dd, J = 4.8, 1.2 Hz, 1H), 8.02 (s, 1H), 8.00-7.90 (M, 1H), 7.38 (dd, J = 7.8, 4.8 Hz, 1H), 5.80-5.40 (m, 2H), 4.70-4.50 (m, 1H) , 4.00-3.60 (m, 6H), 3.10-2.70 (m, 3H), 2.50-2.10 (m, 5H), 1.06 (t, J = 7. 5Hz, 3H)
1-170;
8.94 (d, J = 2.1 Hz, 1H), 8.53 (dd, J = 4.8, 1.5 Hz, 1H), 8.04-7.90 (m, 2H), 7.38 (dd, J = 8.7, 4.8 Hz, 1H), 5.75-5.55 (m, 2H), 4.70-4.50 (m, 1H), 4.20-3.70 ( m, 3H), 3.10-2.70 (m, 3H), 2.50-2.20 (m, 8H), 1.07 (t, J = 6.6 Hz, 3H)
1-171;
8.93 (d, J = 2.1 Hz, 1H), 8.56 (d, J = 4.8 Hz, 1H), 8.12 (s, 1H), 8.05-7.95 (m, 1H) ), 7.42 (dd, J = 8.4, 4.8 Hz, 1H), 4.64 (d, J = 16.8 Hz, 1H), 4.41 (d, J = 16.8 Hz, 1H) , 3.88 (t, J = 7.8 Hz, 1H), 3.73 (s, 3H), 2.39 (s, 3H), 2.10-1.90 (m, 1H), 1.90. -1.70 (m, 4H), 1.02 (t, J = 7.2 Hz, 3H)
1-172;
9.00-8.86 (m, 1H), 8.65-8.45 (m, 1H), 8.10-7.85 (m, 2H), 7.45-7.35 (m, 1H) ), 5.24-4.90 (m, 2H), 4.20-3.50 (m, 6H), 2.85-2.45 (m, 3H), 2.35-2.20 (m) , 3H), 1.80-1.45 (m, 3H), 1.30-1.20 (m, 3H)
1-173;
(Isomer ratio 58) 9.00-8.90 (m, 1H), 8.60-8.50 (m, 1H), 8.05-7.90 (m, 2H), 7.46-7 .34 (m, 1H), 5.25 (d, J = 9.6 Hz, 1H), 4.95 (d, J = 9.6 Hz, 1H), 4.68 (q, J = 7.2 Hz, 1H), 3.95-3.65 (m, 5H), 2.77 (brs, 3H), 2.40-2.25 (m, 3H), 1.82-1.40 (m, 3H) 1.30-1.15 (m, 3H)
(Isomer ratio 27) 9.00-8.90 (m, 1H), 8.60-8.50 (m, 1H), 8.05-7.90 (m, 2H), 7.46-7 .34 (m, 1H), 5.25 (d, J = 9.6 Hz, 1H), 4.95 (d, J = 9.6 Hz, 1H), 4.68 (q, J = 7.2 Hz, 1H), 3.95-3.65 (m, 5H), 2.95 (brs, 3H), 2.40-2.25 (m, 3H), 1.82-1.40 (m, 3H) 1.30-1.15 (m, 3H)
(Isomer ratio 15) 9.00-8.90 (m, 1H), 8.60-8.50 (m, 1H), 8.05-7.90 (m, 2H), 7.46-7 .34 (m, 1H), 5.25 (d, J = 9.6 Hz, 1H), 4.95 (d, J = 9.6 Hz, 1H), 4.68 (q, J = 7.2 Hz, 1H), 3.95-3.65 (m, 5H), 3.07 (brs, 3H), 2.40-2.25 (m, 3H), 1.82-1.40 (m, 3H) 1.30-1.15 (m, 3H)
1-174;
8.93 (d, J = 2.7 Hz, 1H), 8.60-8.50 (m, 1H), 8.11 (s, 1H), 8.10-7.90 (m, 1H), 7.41 (dd, J = 8.4, 4.8 Hz, 1H), 4.62 (d, J = 16.5 Hz, 1H), 4.54 (d, J = 16.5 Hz, 1H), 4 .13 (q, J = 7.2 Hz, 1H), 3.75 (s, 3H), 2.38 (s, 3H), 1.83 (s, 3H), 1.49 (d, J = 7 .2Hz, 3H)
1-175;
(Isomer ratio 5) 9.00-8.85 (m, 1H), 8.65-8.55 (m, 1H), 8.04 (s, 1H), 8.05-7.95 (m , 1H), 7.42 (dd, J = 8.4, 4.8 Hz, 1H), 4.58 (s, 2H), 4.25-4.00 (m, 1H), 3.79 (s) , 3H), 2.54 (s, 3H), 2.35 (s, 3H), 1.50 (d, J = 7.2 Hz, 3H)
(Isomer ratio 3) 9.00-8.85 (m, 1H), 8.60-8.50 (m, 1H), 8.16 (s, 1H), 8.00-7.90 (m , 1H), 7.40-7.30 (m, 1H), 4.67 (d, J = 17.1 Hz, 1H), 4.46 (d, J = 17.1 Hz, 1H), 4.25. -4.00 (m, 1H), 3.76 (s, 3H), 2.52 (s, 3H), 2.38 (s, 3H), 1.52 (d, J = 7.2 Hz, 3H) )
1-176;
8.97 (d, J = 2.4 Hz, 1H), 8.55 (dd, J = 4.8, 1.5 Hz, 1H), 8.14 (s, 1H), 8.05-7.95 (M, 1H), 7.39 (dd, J = 8.4, 4.8 Hz, 1H), 4.66 (q, J = 7.2 Hz, 1H), 4.58 (d, J = 17. 1 Hz, 1 H), 4.51 (d, J = 17.1 Hz, 1 H), 3.81 (s, 3 H), 2.85 (s, 3 H), 2.37 (s, 3 H), 1.75 (D, J = 7.2Hz, 3H)
1-177;
9.05-8.80 (m, 1H), 8.70-8.45 (m, 1H), 8.25-7.90 (m, 2H), 7.55-7.30 (m, 1H) ), 4.75-4.35 (m, 2H), 4.20-4.00 (m, 1H), 3.85-3.70 (m, 3H), 2.60-2.35 (m , 6H), 2.35-1.70 (m, 2H), 1.10-0.90 (m, 3H)
1-178;
8.97 (d, J = 2.7 Hz, 1H), 8.55 (dd, J = 4.8, 1.2 Hz, 1H), 8.14 (s, 1H), 8.00-7.90 (M, 1H), 7.38 (dd, J = 8.4, 4.8 Hz, 1H), 4.65-4.45 (m, 3H), 3.78 (s, 3H), 2.83 (S, 3H), 2.38 (s, 3H), 2.30-2.10 (m, 2H), 1.06 (t, J = 7.2 Hz, 3H)
1-179;
(Isomer ratio 10) 8.95-8.85 (m, 1H), 8.54 (dd, J = 4.8, 1.5 Hz, 1H), 8.05-7.90 (m, 2H) 7.39 (dd, J = 8.4, 4.8 Hz, 1H), 5.75-5.25 (m, 2H), 4.20-3.80 (m, 1H), 3.74 ( brs, 3H), 2.40-2.00 (m, 6H), 1.83 (brs, 3H), 1.55-1.35 (m, 3H)
(Isomer ratio 1) 9.00-8.90 (m, 1H), 8.55-8.45 (m, 1H), 8.05-7.90 (m, 2H), 7.45-7 .30 (m, 1H), 5.75-5.25 (m, 2H), 4.20-3.80 (m, 4H), 2.40-1.80 (m, 9H), 1.55 -1.35 (m, 3H)
1-180;
9.00-8.90 (m, 1H), 8.60-8.45 (m, 1H), 8.10-7.90 (m, 2H), 7.45-7.35 (m, 1H) ), 5.70-5.15 (m, 2H), 4.25-4.00 (m, 1H), 3.85-3.70 (m, 3H), 2.70-2.50 (m , 3H), 2.40-2.20 (m, 3H), 2.11 (brs, 3H), 1.85-1.50 (m, 3H)
1-181;
8.96 (d, J = 2.4 Hz, 1H), 8.54 (dd, J = 4.8, 1.2 Hz, 1H), 8.05-7.90 (m, 2H), 7.39 (Dd, J = 8.4, 4.8 Hz, 1H), 5.75-5.35 (m, 2H), 4.66 (q, J = 7.2 Hz, 1H), 3.80 (s, 3H), 2.81 (s, 3H), 2.33 (s, 3H), 2.11 (s, 3H), 1.75 (d, J = 7.2 Hz, 3H)
1-182;
9.00-8.85 (m, 1H), 8.65-8.45 (m, 1H), 8.10-7.85 (m, 2H), 7.45-7.30 (m, 1H) ), 5.80-5.40 (m, 2H), 4.25-4.00 (m, 1H), 3.80-3.65 (m, 6H), 2.70-2.45 (m , 3H), 2.40-2.20 (m, 3H), 1.52 (d, J = 7.2 Hz, 3H)
1-183;
8.91 (d, J = 2.4 Hz, 1H), 8.56 (dd, J = 4.8, 1.5 Hz, 1H), 8.09 (s, 1H), 7.96 (ddd, J = 8.4, 2.4, 1.5 Hz, 1H), 7.40 (dd, J = 8.4, 4.8 Hz, 1H), 4.64 (d, J = 16.8 Hz, 1H), 4.51 (d, J = 16.8 Hz, 1H), 4.12 (q, J = 7.2 Hz, 1H), 4.10-3.90 (m, 2H), 2.37 (s, 3H) ), 1.86 (s, 3H), 1.50 (d, J = 7.2 Hz, 3H), 1.09 (t, J = 7.2 Hz, 3H)
1-184;
8.93 (d, J = 2.4 Hz, 1H), 8.55 (dd, J = 4.8, 1.5 Hz, 1H), 8.08 (s, 1H), 7.97 (ddd, J = 8.4, 2.4, 1.5 Hz, 1H), 7.41 (dd, J = 8.4, 4.8 Hz, 1H), 4.59 (s, 2H), 4.02 (t, J = 4.2 Hz, 2H), 3.58 (s, 2H), 3.32 (t, J = 4.2 Hz, 2H), 3.15 (s, 3H), 2.37 (s, 3H) , 1.87 (s, 3H)
1-185;
8.89 (d, J = 2.7 Hz, 1H), 8.55-8.50 (m, 1H), 8.10-7.85 (m, 2H), 7.45-7.35 (m , 1H), 5.19 (d, J = 9.9 Hz, 1H), 4.98 (d, J = 9.9 Hz, 1H), 3.95-3.65 (m, 6H), 2.45. -2.30 (m, 3H), 2.20-1.90 (m, 2H), 1.80 (s, 3H), 1.25 (m, 3H), 1.03 (t, J = 7 .2Hz, 3H)
1-187;
8.90-8.85 (m, 1H), 8.60-8.45 (m, 1H), 8.10-7.90 (m, 2H), 7.50-7.35 (m, 1H) ), 5.30-4.90 (m, 2H), 4.20-4.00 (m, 2H), 3.80-3.60 (m, 4H), 2.70-2.20 (m , 6H), 2.00-1.70 (m, 2H), 1.30-1.20 (m, 3H), 1.20-0.90 (m, 3H)
1-189;
9.00-8.85 (m, 1H), 8.65-8.45 (m, 1H), 8.10-7.95 (m, 2H), 7.50-7.35 (m, 1H) ), 5.30-4.80 (m, 2H), 4.20-4.00 (m, 1H), 3.55-3.40 (m, 3H), 2.75-2.20 (m , 9H), 2.00-1.70 (m, 2H), 1.15-0.90 (m, 3H)
1-190;
(Isomer ratio 2) 9.00-8.90 (m, 1H), 8.55-8.50 (m, 1H), 8.05-7.90 (m, 2H), 7.45-7 .35 (m, 1H), 5.20-5.10 (m, 1H), 5.00-4.85 (m, 1H), 4.59 (dd, J = 11.1, 5.4 Hz, 1H), 3.77 (s, 3H), 3.50 (s, 3H), 2.76 (s, 3H), 2.40-2.10 (m, 2H), 2.33 (s, 3H) ), 1.07 (t, J = 7.5 Hz, 3H)
(Isomer ratio 1) 9.00-8.90 (m, 1H), 8.55-8.50 (m, 1H), 8.05-7.90 (m, 2H), 7.45-7 .35 (m, 1H), 5.20-5.10 (m, 1H), 5.00-4.85 (m, 1H), 4.59 (dd, J = 11.1, 5.4 Hz, 1H), 3.88 (brs, 3H), 3.48 (s, 3H), 2.88 (s, 3H), 2.40-2.10 (m, 2H), 2.32 (s, 3H) ), 1.20-0.90 (m, 3H)
1-191;
(Isomer ratio 51) 9.02-8.92 (m, 1H), 8.60-8.50 (m, 1H), 8.40-7.94 (m, 2H), 7.45-7 .35 (m, 1H), 5.30-4.60 (m, 3H), 3.87 (brs, 3H), 3.47 (s, 3H), 2.94 (s, 3H), 31 (s, 3H), 1.82-1.42 (m, 3H)
(Isomer ratio 25) 9.02-8.92 (m, 1H), 8.60-8.50 (m, 1H), 8.40-7.94 (m, 2H), 7.45-7 .35 (m, 1H), 5.30-4.60 (m, 3H), 4.05 (s, 3H), 3.38 (s, 3H), 2.78 (s, 3H), 33 (s, 3H), 1.82-1.42 (m, 3H)
(Isomer ratio 24) 9.02-8.92 (m, 1H), 8.60-8.50 (m, 1H), 8.40-7.94 (m, 2H), 7.45-7 .35 (m, 1H), 5.30-4.60 (m, 3H), 3.81 (s, 3H), 3.50 (s, 3H), 3.06 (s, 3H), 26 (s, 3H), 1.82-1.42 (m, 3H)
1-192;
8.89 (d, J = 2.4 Hz, 1H), 8.55-8.50 (m, 1H), 8.05-7.85 (m, 2H), 7.45-7.35 (m , 1H), 5.15 (d, J = 10.5 Hz, 1H), 4.90 (d, J = 10.5 Hz, 1H), 4.10-3.80 (m, 1H), 3.73 (S, 3H), 3.50 (s, 3H), 2.36 (s, 3H), 2.20-1.90 (m, 2H), 1.81 (s, 3H), 1.03 ( t, J = 7.2 Hz, 3H)
1-194;
9.10-8.80 (m, 1H), 8.65-8.55 (m, 1H), 8.35-8.10 (m, 1H), 8.10-7.95 (m, 1H) ), 7.50-7.35 (m, 1H), 4.85-4.60 (m, 2H), 3.80-3.60 (m, 1H), 3.36 (s, 3H), 1.90 (s, 3H), 1.50-1.30 (m, 3H)
1-213;
9.00-8.85 (m, 1H), 8.65-8.55 (m, 1H), 8.25-7.90 (m, 2H), 7.50-7.40 (m, 1H) ), 3.93 (s, 3H), 3.85-3.30 (m, 1H), 3.45-3.30 (m, 3H), 2.00-1.40 (m, 6H)
1-196;
9.00-8.80 (m, 1H), 8.65-8.55 (m, 1H), 8.30-7.90 (m, 2H), 7.50-7.40 (m, 1H) ), 3.85-3.30 (m, 4H), 2.30-2.20 (m, 3H), 2.20-1.35 (m, 6H)
1-197;
8.98 (d, J = 2.7 Hz, 1H), 8.59 (s, 1H), 8.49 (dd, J = 4.8, 1.5 Hz, 1H), 8.32 (brs, 1H) ), 7.97 (ddd, J = 8.7, 2.7.1.5 Hz, 1H), 7.36 (dd, J = 8.7, 4.8 Hz, 1H), 3.96 (s, 3H), 2.35 (s, 3H), 2.14 (s, 3H), 1.55 (s, 6H)
1-198;
9.00-8.85 (m, 1H), 8.65-8.40 (m, 2H), 8.10-7.90 (m, 1H), 7.50-7.30 (m, 1H) ), 5.35 (m, 2H), 3.55-3.30 (m, 7H), 1.90-1.75 (m, 3H), 1.65-1.30 (m, 3H)
1-200;
8.97 (d, J = 2.7 Hz, 1H), 8.77 (brs, 1H), 8.58 (s, 1H), 8.49 (dd, J = 4.8, 1.5 Hz, 1H) ), 7.98 (ddd, J = 7.8, 2.7.1.5 Hz, 1H), 7.36 (dd, J = 7.8, 4.8 Hz, 1H), 4.03 (s, 3H), 3.08 (s, 3H), 2.35 (s, 3H), 1.74 (s, 6H)
1-203;
8.98 (d, J = 2.7 Hz, 1H), 8.54 (s, 1H), 8.50 (dd, J = 4.8, 1.5 Hz, 1H), 7.98 (ddd, J = 8.1, 2.7, 1.5 Hz, 1H), 7.93 (s, 1H), 7.78 (d, J = 8.4 Hz, 2H), 7.37 (dd, J = 8. 1,4.8 Hz, 1H), 7.29 (d, J = 8.4 Hz, 2H), 5.59 (dd, J = 8.7, 6.0 Hz, 1H), 4.06 (s, 3H) ), 2.41 (s, 3H), 2.35 (s, 3H), 2.25-2.10 (m, 1H), 2.00-1.80 (m, 1H), 0.87 ( t, J = 7.2 Hz, 3H)
1-205;
9.01-8.97 (m, 1H), 8.72-8.66 (m, 1H), 8.63 (s, 1H), 8.52-8.48 (m, 1H), 8. 31 (brs, 1H), 8.02-7.95 (m, 1H), 7.69-7.62 (m, 1H), 7.41-7.33 (m, 1H), 7.30- 7.23 (m, 1H), 5.75 (t, J = 7.8 Hz, 1H), 4.13 (s, 3H), 2.37 (s, 3H), 2.22-2.00 ( m, 2H), 1.03 (t, J = 7.2 Hz, 3H)
1-207;
(Isomer ratio 2) 8.96 (d, J = 2.4 Hz, 1H), 8.59 (s, 1H), 8.56-8.44 (m, 2H), 8.20-7.92 (M, 1H), 7.71-7.65 (m, 1H), 7.71-7.65 (m, 5H), 4.09 (s, 3H), 2.43 (s, 3H)
(Isomer ratio 1) 8.99 (d, J = 1.8 Hz, 1H), 8.67 (s, 1H), 8.56-8.44 (m, 1H), 8.20-7.92 (M, 2H), 7.71-7.65 (m, 6H), 4.11 (s, 3H), 2.36 (s, 3H)
1-208;
9.00 (brs, 1H), 8.67 (brs, 1H), 8.07 (s, 1H), 8.02 (d, J = 8.7 Hz, 1H), 7.45 (brs, 1H) , 3.91 (s, 3H), 3.71 (q, J = 6.9 Hz, 1H), 2.10 (s, 3H), 2.06 (s, 3H), 1.48 (d, J = 6.9Hz, 3H)
1-212;
8.98 (d, J = 3.0 Hz, 1H), 8.70-8.60 (m, 1H), 8.54 (s, 1H), 8.45 (dd, J = 4.8, 1 .2 Hz, 1H), 8.00 (ddd, J = 8.4, 3.0, 1.2 Hz, 1H), 7.86 (t, J = 4.5 Hz, 1H), 7.35 (dd, J = 8.4, 4.8 Hz, 1H), 4.75-4.60 (m, 1H), 3.50-3.30 (m, 2H), 2.37 (s, 3H), 2. 15-1.70 (m, 5H), 1.27 (t, J = 7.2 Hz, 3H), 0.99 (t, J = 7.2 Hz, 3H)
1-218;
9.82 (s, 1H), 9.00 (d, J = 2.7 Hz, 1H), 8.60 (s, 1H), 8.50 (dd, J = 4.8, 1.2 Hz, 1H) ), 8.01 (ddd, J = 8.4, 2.7, 1.2 Hz, 1H), 7.40-6.75 (m, 7H), 3.80-3.65 (m, 1H) , 2.40 (s, 3H), 2.14 (s, 3H), 2.10-1.85 (m, 2H), 1.07 (t, J = 7.2 Hz, 3H)
1-222;
8.98 (d, J = 2.4 Hz, 1H), 8.83 (brs, 1H), 8.61 (s, 1H), 8.53 (dd, J = 4.8, 1.0 Hz, 1H) ), 8.07 (t, J = 4.5 Hz, 1H), 7.99 (ddd, J = 8.4, 2.4, 1.0 Hz, 1H), 7.38 (dd, J = 8. 4, 4.8 Hz, 1 H), 6.05-5.85 (m, 1 H), 5.35-5.20 (m, 2 H), 4.78 (q, J = 7.5 Hz, 1 H), 4.10-4.00 (m, 2H), 2.02 (s, 3H), 1.47 (d, J = 7.5 Hz, 3H)
1-225;
(Isomer ratio 3) 8.97 (d, J = 2.4 Hz, 1H), 8.59 (s, 1H), 8.47 (dd, J = 4.8, 1.2 Hz, 1H), 8 .37 (brs, 1H), 7.9-7.95 (m, 1H), 7.35 (dd, J = 8.1, 4, 8 Hz, 1H), 5.90-5.68 (m, 1H), 5.20-5.04 (m, 2H), 4.06 (s, 3H), 3.16 (d, J = 8.1 Hz, 2H), 2.72-2.51 (m, 1H), 2.37 (s, 3H), 2.14-1.77 (m, 2H), 0.97 (t, J = 8.4 Hz, 3H)
(Isomer ratio 1) 8.97 (d, J = 2.4 Hz, 1H), 8.59 (s, 1H), 8.47 (dd, J = 4.8, 1.2 Hz, 1H), 8 .39 (brs, 1H), 7.9-7.95 (m, 1H), 7.35 (dd, J = 8.1, 4, 8 Hz, 1H), 5.90-5.68 (m, 1H), 5.20-5.04 (m, 2H), 4.06 (s, 3H), 3.11 (d, J = 8.1 Hz, 2H), 2.72-2.51 (m, 1H), 2.37 (s, 3H), 2.14-1.77 (m, 2H), 1.07-0.95 (m, 3H)
1-231;
10.3 (brs, 1H), 8.98 (d, J = 2.4 Hz, 1H), 8.58 (s, 1H), 8.52 (dd, J = 4.8, 1.2 Hz, 1H) ), 8.05-7.90 (m, 1H), 7.45-7.20 (m, 7H), 5.26 (s, 2H), 4.01 (q, J = 7.2 Hz, 1H) ), 2.39 (s, 3H), 2.20 (s, 3H), 1.58 (d, J = 7.2 Hz, 3H)
―――――――――――――――――――――――――――――――――――――――
The proton nuclear magnetic resonance chemical shift values in Table 3 are Me as reference materials. ₄ Measurement was performed at 300 MHz using Si (tetramethylsilane).

A part of the optically active form of the compound of the present invention was separated into the optically active form using high performance liquid chromatography having an optically active column. The method will be described in detail, but the present invention is not limited to these.
(A) Separation of optically active substance For high performance liquid chromatography, Shimadzu Corporation; 10AVP system was used.

  The optically active substance was separated according to the conditions described below.

Flow rate: 7.0 ml / min Oven temperature: 40 ° C
Mobile phase: n-hexane: ethanol = 85: 15 (volume ratio)
Column: Daicel CHIRALPAK AD-H (inner diameter 20 mm, length 250 mm, particle diameter 5 μm),
Measurement wavelength: 254 nm
N- {3-chloro-1- (pyridin-3-yl) -1H-pyrazol-4-yl} -N- (cyanomethyl) -2- (methoxyimino) -3- (methylthio) butanamide (present compound 1 -071) (600 mg) was dissolved in 2 ml of a mixed solvent of n-hexane: ethanol = 9: 1 (volume ratio), and this solution was divided into 0.1 ml and subjected to high performance liquid chromatography under the conditions described above. Separation work was performed 15 times in total, and fractions corresponding to peaks with a retention time of 39.5 min and a retention time of 43.3 min were collected. After the solvent of each fraction was distilled off under reduced pressure, 62.5 mg of a colorless transparent oil {[α] _D ^23.5 -41.23 ° (CHCl ₃ , c = 0.624)}, and 65.8 mg of a yellow oil {[α] _D ^23.6 + 34.88 ° (CHCl ₃ , c = 0.734)} was obtained from the fraction having a retention time of 43.3 min.
(B) Determination of optical purity Furthermore, optical purity was measured for the obtained target object using the high performance liquid chromatography which has an optically active column.

  For high performance liquid chromatography, JASCO Corporation; LC-2000 system was used.

  The measurement was performed according to the conditions described below.

Flow rate: 0.6 ml / min Oven temperature: 30 ° C
Mobile phase: n-hexane: ethanol = 9: 1 (volume ratio)
Column: Daicel CHIRALPAK AD-3 (inner diameter 2.1 mm, length 250 mm, particle diameter 5 μm),
Measurement wavelength: 254 nm
As a result,
<1> Retention time 12.0 min [62.5 mg of a colorless transparent oil obtained from the fraction having a retention time of 39.5 min in the above (A) {[α] _D ^23.5 -41.23 ° (CHCl ₃ , c = 0.624) }] 99.9% (99% ee) and
<2> Retention time 15.3 min [65.8 mg of yellow oil obtained from the fraction with retention time 43.3 min in the above (A) {[α] _D ^23.6 + 34.88 ° (CHCl ₃ , c = 0.734)} A fraction corresponding to a peak of 98.6% (97.1% ee) was detected.
[Test example]
Next, the usefulness of the compound of the present invention as a pest control agent will be specifically described in the following test examples, but the present invention is not limited to these.
Test Example 1 Insecticidal test against brown planthopper A 10% emulsion of the compound of the present invention (depending on the compound, 10% wettable powder) was diluted with water containing a spreading agent to prepare a chemical solution having a concentration of 500 ppm. Rice leaf sheaths are immersed in this chemical solution for about 10 seconds, air-dried and placed in a test tube, and 5 second-instar larvae of the green planthopper (Nilaparvata lugens) are released per test tube and covered with a sponge. Housed in a constant temperature room. The number of dead insects after 6 days was investigated, and the death rate (%) (number of dead insects ÷ number of test insects × 100) was calculated. In addition, the test was performed by 2 continuous systems.

As a result, among the compounds tested, the following compounds showed a death rate of 90% or more.
Compounds of the present invention: 1-001, 1-002, 1-004, 1-006, 1-009 to 1-014, 1-015, 1-016, 1-018 to 1-021, 1-024, 1- 027 to 1-035, 1-037, 1-038, 1-039, 1-041 to 1-048, 1-050 to 1-185, 1-187 to 1-195, 1-197 to 1-209, 1-211-1-231, 1-018 (* 3), 1-020 (* 3), 1-056 (* 3), 1-057 (* 3), 1-077 (* 3), 1- 090 (* 3), 1-091 (* 3), 1-105 (* 3), 1-116 (* 3), 1-217 (* 3), 1-228 (* 3), 1-231 ( * 3), 1-056 (+), 1-056 (-), 1-057 (+), 1-057 (-), 1-116 (+), 1-116 ( ), 1-141 (+), 1-141 (-)
Test Example 2 Insecticidal test against silver leaf whitefly A moist filter paper was laid on a 7 cm inner diameter styrol cup, and a green leaf cut into 3 cm was placed thereon. A 10% emulsion of a compound of the present invention (depending on the compound, 10% wettable powder) is diluted with water containing a spreading agent to prepare a chemical solution with a concentration of 500 ppm, and the chemical solution is prepared using a rotary spray tower. 2.5 ml was sprayed per styrene cup (2.5 mg / cm 2). After the leaves were air-dried, adults of silver leaf whiteflies (Bemisia argentifolii) were released, covered, and housed in a thermostatic chamber at 25 ° C. The number of dead insects after 5 days was investigated, and the dead insect rate was calculated from the same calculation formula as in Test Example 1. In addition, the test was performed by 2 continuous systems.

As a result, among the compounds tested, the following compounds showed a death rate of 90% or more.
Compounds of the present invention: 1-002, 1-010, 1-011, 1-012, 1-015, 1-019, 1-021, 1-024, 1-026 to 1-034, 1-037, 1- 038, 1-039, 1-041 to 1-053, 1-055, 1-056, 1-057, 1-059, 1-061, 1-062, 1-065, 1-066, 1-068, 1-069, 1-071-1-077, 1-079, 1-081-1-088, 1-090-1-093, 1-095-1-098, 1-102-1-107, 1- 109, 1-111, 1-112, 1-113, 1-115 to 1-145, 1-147 to 151, 1-154, 1-155, 1-156, 1-158 to 1-185, 1-187 to 1-192, 1-194, 1-195, 1-198, 1- 99, 1-201, 1-202, 1-204, 1-206 to 1-209, 1-211, 1-212, 1-213, 1-214, 1-216 to 1-220, 1-222, 1-223, 1-225, 1-226, 1-228 to 1-230, 1-056 (* 3), 1-057 (* 3), 1-077 (* 3), 1-090 (* 3) ), 1-091 (* 3), 1-105 (* 3), 1-116 (* 3), 1-217 (* 3), 1-228 (* 3), 1-056 (+), 1 -056 (-), 1-057 (+), 1-057 (-), 1-116 (+), 1-116 (-), 1-141 (+), 1-141 (-)
Test Example 3 Insecticidal test against peach aphid A moist absorbent cotton was laid on a glass petri dish with an inner diameter of 3 cm, and kanran leaves cut out to the same diameter were placed on it. did. One day later, a 10% emulsion of the compound of the present invention (depending on the compound, 10% wettable powder was tested) was diluted with water containing a spreading agent to prepare a chemical solution with a concentration of 500 ppm. The chemical solution was sprayed (2.5 mg / cm ² ), covered, and stored in a constant temperature room at 25 ° C. The number of dead insects after 6 days was investigated, and the death rate was calculated from the same calculation formula as in Test Example 1. In addition, the test was performed by 2 continuous systems.

As a result, among the compounds tested, the following compounds showed a death rate of 90% or more.
Compounds of the present invention: 1-001 to 1-004, 1-006 to 1-024, 1-026 to 1-185, 1-187 to 1-192, 1-194, 1-195, 1-197 to 1- 223, 1-225-1-231, 1-014 (* 3), 1-018 (* 3), 1-020 (* 3), 1-056 (* 3), 1-057 (* 3), 1-077 (* 3), 1-090 (* 3), 1-091 (* 3), 1-105 (* 3), 1-116 (* 3), 1-217 (* 3), 1- 228 (* 3), 1-231 (* 3), 1-056 (+), 1-056 (-), 1-057 (+), 1-057 (-), 1-116 (+), 1 -116 (-), 1-141 (+), 1-141 (-)
Test Example 4 Insecticidal test for cotton aphids Wet cotton wool with a 3 cm inner diameter petri dish and a cucumber leaf cut out to the same diameter were placed on it, and four cotton aphids (Aphis gossypii) adults were released. One day later, a 10% emulsion of the compound of the present invention (depending on the compound, 10% wettable powder was tested) was diluted with water containing a spreading agent to prepare a chemical solution with a concentration of 100 ppm. The chemical solution was sprayed (2.5 mg / cm ² ), covered, and stored in a constant temperature room at 25 ° C. The number of dead insects after 6 days was investigated, and the death rate was calculated from the same calculation formula as in Test Example 1. In addition, the test was performed by 2 continuous systems.

As a result, among the compounds tested, the following compounds showed a death rate of 90% or more.
Compounds of the present invention: 1-001, 1-002, 1-006 to 1-021, 1-026 to 1-035, 1-037 to 1-057, 1-059 to 1-111, 1-113, 1- 115-119, 1-121-1-145, 1-147-1-157, 1-159-1-185, 1-187-1-192, 1-194, 1-197, 1-198, 1-201-223, 1-225-1-231, 1-014 (* 3), 1-018 (* 3), 1-020 (* 3), 1-056 (* 3), 1- 057 (* 3), 1-077 (* 3), 1-090 (* 3), 1-091 (* 3), 1-105 (* 3), 1-116 (* 3), 1-217 ( * 3) 1-228 (* 3), 1-231 (* 3), 1-056 (+), 1-056 (-), 1-057 (+), 1- 057 (-), 1-116 (+), 1-116 (-), 1-141 (+), 1-141 (-)
Test Example 5 Soil irrigation treatment test for peach aphid A 10% emulsion of the compound of the present invention was diluted with tap water to prepare a chemical solution having a concentration of 100 ppm.

10 ml of the chemical solution was irrigated to the stock soil portion of the plastic cup planted cabbage seedling (2.5 true leaf stage) and left in the greenhouse. One day after the irrigation treatment, 20 mosquitoes / strain of adult peach aphid (Myzus persicae) were released and then left in the greenhouse. The number of surviving insects 6 days after the release was examined, and a control value was calculated from the following formula.
Control value (%) = {1- (Cb × Tai) / (Cai × Tb)} × 100
The characters in the formula represent the following:
Cb: number of insects before treatment in the untreated group Cai: number of live insects at the time of final survey in the untreated group Tb: number of insects before treatment in the treated group Tai: number of live insects at the time of final survey in the treated group Among the compounds tested, the following compounds showed a control value of 90% or more.
Compounds of the present invention: 1-001, 1-002, 1-010, 1-011, 1-012, 1-017, 1-018, 1-019, 1-027 to 1-034, 1-038, 1- 041-1-046, 1-048, 1-049, 1-056-1-059, 1-061, 1-062, 1-063, 1-065, 1-066, 1-068, 1-072- 1-077, 1-079, 1-081 to 1-091, 1-095 to 1-098, 1-102 to 1-107, 1-113, 1-115 to 1-119, 1-121, 1- 122, 1-124-1-127, 1-130, 1-131, 1-133, 1-135-139, 1-141, 1-155, 1-156, 1-160, 1-161, 1-163, 1-164, 1-168, 1-169, 1-172, 1- 73, 1-174, 1-179, 1-181, 1-185, 1-188, 1-191, 1-199, 1-201, 1-202, 1-211, 1-213, 1-223, 1-225, 1-228 to 1-230, 1-056 (* 3), 1-057 (* 3), 1-077 (* 3), 1-090 (* 3), 1-091 (* 3) ), 1-105 (* 3), 1-116 (* 3), 1-228 (* 3), 1-056 (+), 1-056 (-), 1-057 (+), 1-057 (-), 1-116 (+), 1-116 (-), 1-141 (+), 1-141 (-)
Test Example 6 Effect test on cat fleas 3.5 mg of the compound of the present invention was dissolved in 3.5 ml of acetone to prepare a chemical solution having a concentration of 1000 ppm. After 350 μl of this chemical solution was applied to the bottom and side surfaces of a glass container having an inner wall surface area of 35 cm ² , acetone was volatilized to form a thin film of pyrazole derivative on the inner wall of the glass container. Since the inner wall of the used glass container is 35 cm ² , the treatment dose is 10 μg / cm ² . Five cat fleas (Ctenocephalides felis) adults (mixed males and females) were released on this, covered, and housed in a thermostatic chamber at 25 ° C. After 4 days, the number of insects with behavioral abnormalities was investigated, and the efficiency (%) was calculated from the following formula. In addition, the test was performed by 2 continuous systems.

efficacy (%) = (number of insects with behavioral abnormalities derived from compounds / number of worms) × 100
As a result, among the compounds tested, the following compounds showed an efficiency (%) of 80% or more (not evaluated after 1-210).
Compounds of the present invention: 1-001, 1-004, 1-007, 1-010, 1-011, 1-012, 1-014, 1-015, 1-016, 1-017, 1-019, 1- 021, 1-024, 1-026, 1-027, 1-028, 1-029, 1-030, 1-031, 1-032, 1-033, 1-034, 1-035, 1-036, 1-037, 1-038, 1-039, 1-040, 1-041, 1-042, 1-043, 1-044, 1-045, 1-046, 1-047, 1-048, 1- 049, 1-050, 1-051, 1-052, 1-053, 1-054, 1-055, 1-056, 1-059, 1-066, 1-068, 1-069, 1-070, 1-071, 1-072, 1-074, 1-077, 1-079, 1- 81, 1-082, 1-083, 1-085, 1-086, 1-087, 1-088, 1-089, 1-094, 1-095, 1-096, 1-097, 1-099, 1-100, 1-101, 1-102, 1-103, 1-104, 1-105, 1-106, 1-107, 1-108, 1-109, 1-110, 1-113, 1- 115, 1-117, 1-118, 1-121, 1-123, 1-124, 1-126, 1-129, 1-131, 1-133, 1-136, 1-137, 1-139, 1-146, 1-147, 1-148, 1-150, 1-151, 1-152, 1-153, 1-154, 1-155, 1-156, 1-157, 1-161, 1- 164, 1-166, 1-169, 1-171, 1-174, 1-175 1-176, 1-177, 1-179, 1-181, 1-184, 1-186, 1-187, 1-189, 1-190, 1-191, 1-192, 1-193, 1- 194, 1-197, 1-199, 1-200, 1-201, 1-202, 1-203, 1-204, 1-205, 1-206, 1-207, 1-208, 1-209, 1-014 (* 3), 1-056-(+), 1-057-(+), 1-057 (* 3) 1-077 (* 3), 1-116 (-), 1-141 ( −)
Test Example 7 Effect test on tick (American dog tick) 3.5 mg of the compound of the present invention was dissolved in 3.5 ml of acetone to prepare a chemical solution having a concentration of 1000 ppm. After 350 μl of this chemical solution was applied to the bottom and side surfaces of a glass container having an inner wall surface area of 35 cm ² , acetone was volatilized to form a thin film of pyrazole derivative on the inner wall of the glass container. Since the inner wall of the used glass container is 35 cm ² , the treatment dose is 10 μg / cm ² . Five American dog tick (Dermacentor variabilis) first nymphs (mixed males and females) were released, covered, and housed in a thermostatic chamber at 25 ° C. The number of insects in which behavioral abnormalities were observed after 4 days was investigated, and the efficiency (%) was calculated from the same calculation formula as in Test Example 6. In addition, the test was performed by 2 continuous systems.

As a result, among the tested compounds, the following compounds showed an efficiency (%) of 80% or more (not evaluated after 1-210).
Compounds of the present invention: 1-056, 1-059, 1-115, 1-146, 1-171, 1-187, 1-197, 1-141 (−)

  The novel pyrazole derivative in the present invention exhibits excellent pest control activity, particularly insecticidal / miticidal activity, and is extremely useful with little adverse effect on non-target organisms such as mammals, fish and beneficial insects. A compound.

Claims (10)

Formula (1):

[Where A ¹ Is -N (-O) _m2 Or -CR ¹ Represents
R ¹ , R ³ And R ⁴ Each independently represents a hydrogen atom, a halogen atom, cyano, nitro, -OH, -SH, -NH ₂ , -CHO, -C (O) OH, -C (O) NH ₂ , -C (S) NH ₂ , -S (O) ₂ NH ₂ , C ₁ ~ C ₆ Alkyl, R ^28a Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, C ₃ ~ C ₈ Cycloalkyl, R ^28a Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkyl, C ₂ ~ C ₆ Alkenyl, R ^28a Optionally substituted with (C ₂ ~ C ₆ ) Alkenyl, C ₃ ~ C ₈ Cycloalkenyl, R ^28a Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkenyl, C ₂ ~ C ₆ Alkynyl, R ^28a Optionally substituted with (C ₂ ~ C ₆ ) Alkynyl, C ₁ ~ C ₆ Alkoxy, C ₁ ~ C ₆ Haloalkoxy, C ₁ ~ C ₆ Alkylthio, C ₁ ~ C ₆ Alkylsulfinyl, C ₁ ~ C ₆ Alkylsulfonyl, C ₁ ~ C ₆ Haloalkylthio, C ₁ ~ C ₆ Haloalkylsulfinyl, C ₁ ~ C ₆ Haloalkylsulfonyl, C ₁ ~ C ₆ Alkylcarbonyl, C ₃ ~ C ₈ Cycloalkylcarbonyl, C ₁ ~ C ₆ Haloalkylcarbonyl, C ₃ ~ C ₈ Halocycloalkylcarbonyl, C ₁ ~ C ₆ Alkoxycarbonyl, C ₁ ~ C ₆ Haloalkoxycarbonyl, C ₁ ~ C ₆ Alkylaminosulfonyl, di (C ₁ ~ C ₆ Alkyl) aminosulfonyl, C ₁ ~ C ₆ Alkylaminocarbonyl, di (C ₁ ~ C ₆ Alkyl) aminocarbonyl, C ₁ ~ C ₆ Alkylamino or di (C ₁ ~ C ₆ Alkyl) amino,
R ² Is a halogen atom, cyano, nitro, -OH, -SH, -NH ₂ , -CHO, -C (O) OH, -C (O) NH ₂ , -C (S) NH ₂ , -S (O) ₂ NH ₂ , C ₁ ~ C ₆ Alkyl, R ^28a Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, C ₃ ~ C ₈ Cycloalkyl, R ^28a Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkyl, C ₂ ~ C ₆ Alkenyl, R ^28a Optionally substituted with (C ₂ ~ C ₆ ) Alkenyl, C ₃ ~ C ₈ Cycloalkenyl, R ^28a Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkenyl, C ₂ ~ C ₆ Alkynyl, R ^28a Optionally substituted with (C ₂ ~ C ₆ ) Alkynyl, C ₁ ~ C ₆ Alkoxy, C ₁ ~ C ₆ Haloalkoxy, C ₁ ~ C ₆ Alkylthio, C ₁ ~ C ₆ Alkylsulfinyl, C ₁ ~ C ₆ Alkylsulfonyl, C ₁ ~ C ₆ Haloalkylthio, C ₁ ~ C ₆ Haloalkylsulfinyl, C ₁ ~ C ₆ Haloalkylsulfonyl, C ₁ ~ C ₆ Alkylcarbonyl, C ₃ ~ C ₈ Cycloalkylcarbonyl, C ₁ ~ C ₆ Haloalkylcarbonyl, C ₃ ~ C ₈ Halocycloalkylcarbonyl, C ₁ ~ C ₆ Alkoxycarbonyl, C ₁ ~ C ₆ Haloalkoxycarbonyl, C ₁ ~ C ₆ Alkylaminosulfonyl, di (C ₁ ~ C ₆ Alkyl) aminosulfonyl, C ₁ ~ C ₆ Alkylaminocarbonyl, di (C ₁ ~ C ₆ Alkyl) aminocarbonyl, C ₁ ~ C ₆ Alkylamino or di (C ₁ ~ C ₆ Alkyl) amino, and when n represents an integer of 2 or more, each R ² May be the same or different from each other,
R ^a Is a hydrogen atom, C ₁ ~ C ₆ Alkyl, R ^5a Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, C ₂ ~ C ₆ Alkenyl, R ^5a Optionally substituted with (C ₂ ~ C ₆ ) Alkenyl, C ₂ ~ C ₆ Alkynyl, R ^5a Optionally substituted with (C ₂ ~ C ₆ ) Alkynyl, -S (O) _r2 R ^6a , -C (O) OR ^6a , -C (O) SR ^6a , -C (S) OR ^6a , -C (S) SR ^6a , -C (O) R ^7a , -C (S) R ^7a , -C (O) N (R ^8a ) R ^9a Or -C (S) N (R ^8a ) R ^9a Represents
R ^b Is -C (O) R ^7b Or -C (S) R ^7b Represents
R ^5a Is a halogen atom, cyano, C ₃ ~ C ₈ Cycloalkyl, -OR ^11a , -S (O) _r2 R ^11a , -N (R ^13a ) R ^14a , -C (O) OH, -C (O) OR ^11a , -C (O) SR ^11a , -C (S) OR ^11a , -C (S) SR ^11a , -C (O) R ^12a , -C (S) R ^12a , -C (O) N (R ^13a ) R ^14a , -C (S) N (R ^13a ) R ^14a , Phenyl, (Z) _q Phenyl, naphthyl, substituted by (Z) _q Naphthyl substituted by, D1-2, D1-7, D1-8, D1-10, D1-32, D1-33, D1-34, D1-36, D1-37, D1-38, D1-79, D1-80, D1-81, D1-82, D1-84, D1-85, D1-87, D1-92, D1-93, D1-95, D1-96 or D1-98,
R ^6a Is C ₁ ~ C ₆ Alkyl or R ^10a Optionally substituted with (C ₁ ~ C ₆ ) Represents alkyl,
R ^7a Is a hydrogen atom, C ₁ ~ C ₆ Alkyl, C ₃ ~ C ₈ Cycloalkyl, R ^10a Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, -C (O) OH, -C (O) OR ^11a , -C (O) R ^12a , -C (S) R ^12a , -C (O) N (R ^13a ) R ^14a , -C (S) N (R ^13a ) R ^14a ,, -C (= NR ^13a ) R ^12a , -C (= NOH) R ^12a , -C (= NOR ^11a ) R ^12a Or -C {= NN (R ^13a ) R ^14a } R ^12a Represents
R ^7b Is -C (= NOH) R ^12b , -C (= NOR ^11b ) R ^12b Or -C {= NN (R ^13b ) R ^14b } R ^12b Represents
R ^8a Is a hydrogen atom, C ₁ ~ C ₆ Alkyl, R ^10a Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, C ₃ ~ C ₈ Cycloalkyl, R ^10a Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkyl, -OR ^11a , -S (O) _r2 R ^11a , D1-32, D1-33, D1-34 or D1-37,
R ^9a Is a hydrogen atom, C ₁ ~ C ₆ Alkyl, R ^10a Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, -S (O) _r2 R ^11a Or -C (O) R ^12a Represents
R ^10a Is a halogen atom, cyano, nitro, C ₃ ~ C ₈ Cycloalkyl, C ₃ ~ C ₈ Halocycloalkyl, —OH, —OR ^11a , -SH or -S (O) _r2 R ^11a Represents
R ^11a Is C ₁ ~ C ₆ Alkyl, R ^15a Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, C ₂ ~ C ₆ Alkenyl, R ^15a Optionally substituted with (C ₂ ~ C ₆ ) Alkenyl, C ₃ ~ C ₈ Cycloalkenyl, R ^15a Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkenyl, C ₂ ~ C ₆ Alkynyl, R ^15a Optionally substituted with (C ₂ ~ C ₆ ) Alkynyl, C ₃ ~ C ₈ Cycloalkyl, R ^15a Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkyl, -C (O) OR ^16a , -C (O) SR ^16a , -C (S) OR ^16a , -C (S) SR ^16a , -C (O) R ^17a , -C (S) R ^17a , -C (O) N (R ^18a ) R ^19a , -C (S) N (R ^18a ) R ^19a , Phenyl, (Z) _q Phenyl, naphthyl, substituted by (Z) _q Naphthyl substituted by D1-2, D1-32, D1-33, D1-34, D1-36, D1-37, D1-38, D1-79, D1-80, D1-81, D1-82, D1-84, D1-85, D1-87, D1-92, D1-93, D1-95, D1-96 or D1-98,
R ^11b Is C ₁ ~ C ₆ Alkyl, R ^15b Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, C ₂ ~ C ₆ Alkenyl, R ^15b Optionally substituted with (C ₂ ~ C ₆ ) Alkenyl, C ₃ ~ C ₈ Cycloalkenyl, R ^15b Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkenyl, C ₂ ~ C ₆ Alkynyl, R ^15b Optionally substituted with (C ₂ ~ C ₆ ) Alkynyl, C ₃ ~ C ₈ Cycloalkyl, R ^15b Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkyl, -S (O) _r3 R ^16b , -C (O) OR ^16b , -C (O) SR ^16b , -C (S) OR ^16b , -C (S) SR ^16b , -C (O) R ^17b , -C (S) R ^17b , -C (O) N (R ^18b ) R ^19b , -C (S) N (R ^18b ) R ^19b , Phenyl, (Z) _q Phenyl, naphthyl, substituted by (Z) _q Naphthyl substituted by, D1-2, D1-7, D1-8, D1-10, D1-32, D1-33, D1-34, D1-36, D1-37, D1-38, D1-79, D1-80, D1-81, D1-82, D1-84, D1-85, D1-87, D1-92, D1-93, D1-95, D1-96 or D1-98,
R ^12a Is a hydrogen atom, halogen atom, cyano, C ₁ ~ C ₆ Alkyl, R ^15a Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, C ₂ ~ C ₆ Alkenyl, R ^15a Optionally substituted (C ₂ ~ C ₆ ) Alkenyl, C ₃ ~ C ₈ Cycloalkenyl, R ^15a Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkenyl, C ₂ ~ C ₆ Alkynyl, R ^15a Optionally substituted with (C ₂ ~ C ₆ ) Alkynyl, C ₃ ~ C ₈ Cycloalkyl, R ^15a Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkyl, -OR ^16a , -S (O) _r2 R ^16a , -C (O) R ^17a , Phenyl, (Z) _q Phenyl, naphthyl, substituted by (Z) _q Naphthyl substituted by, D1-2, D1-7, D1-8, D1-10, D1-32, D1-33, D1-34, D1-36, D1-37, D1-38, D1-79, D1-80, D1-81, D1-82, D1-84, D1-85, D1-87, D1-92, D1-93, D1-95, D1-96 or D1-98,
R ^12b Is a hydrogen atom, halogen atom, cyano, C ₁ ~ C ₆ Alkyl, R ^15c Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, C ₂ ~ C ₆ Alkenyl, R ^15c Optionally substituted (C ₂ ~ C ₆ ) Alkenyl, C ₃ ~ C ₈ Cycloalkenyl, R ^15c Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkenyl, C ₂ ~ C ₆ Alkynyl, R ^15c Optionally substituted with (C ₂ ~ C ₆ ) Alkynyl, C ₃ ~ C ₈ Cycloalkyl, R ^15c Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkyl, -OR ^16c , -S (O) _r R ^16c , -C (O) OR ^16c , -C (O) SR ^16c , -C (S) OR ^16c , -C (S) SR ^16c , -C (O) R ^17c , -C (S) R ^17c , -C (O) N (R ^18c ) R ^19c , -C (S) N (R ^18c ) R ^19c , -C (= NOH) R ^17c , -C (= NOR ^16c ) R ^17c , -C {= NN (R ^18c ) R ^19c } R ^17c , Phenyl, (Z) _q Phenyl, naphthyl, substituted by (Z) _q Naphthyl substituted by, D1-2, D1-7, D1-8, D1-10, D1-32, D1-33, D1-34, D1-36, D1-37, D1-38, D1-79, D1-80, D1-81, D1-82, D1-84, D1-85, D1-87, D1-92, D1-93, D1-95, D1-96 or D1-98,
R ^13a And R ^14a Each independently represents a hydrogen atom or C ₁ ~ C ₆ Represents alkyl,
R ^13b Is a hydrogen atom, cyano, nitro, C ₁ ~ C ₆ Alkyl, R ^15b Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, C ₂ ~ C ₆ Alkenyl, R ^15b Optionally substituted with (C ₂ ~ C ₆ ) Alkenyl, C ₃ ~ C ₈ Cycloalkenyl, R ^15b Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkenyl, C ₂ ~ C ₆ Alkynyl, R ^15b Optionally substituted with (C ₂ ~ C ₆ ) Alkynyl, C ₃ ~ C ₈ Cycloalkyl, R ^15b Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkyl, -OR ^16b , -S (O) _r3 R ^16b , -C (O) OR ^16b , -C (O) SR ^16b , -C (S) OR ^16b , -C (S) SR ^16b , -C (O) R ^17b , -C (S) R ^17b , -C (O) N (R ^18b ) R ^19b , -C (S) N (R ^18b ) R ^19b , -S (O) _r3 N (R ^18b ) R ^19b , Phenyl, (Z) _q Phenyl, naphthyl, substituted by (Z) _q Naphthyl substituted by, D1-2, D1-7, D1-8, D1-10, D1-32, D1-33, D1-34, D1-36, D1-37, D1-38, D1-79, D1-80, D1-81, D1-82, D1-84, D1-85, D1-87, D1-92, D1-93, D1-95, D1-96 or D1-98 or R1- ^13b Is R ^14b Together with C ₂ ~ C ₇ An alkylene chain or C ₂ ~ C ₇ By forming an alkenylene chain of R ^13b And R ^14b May form a 3- to 8-membered ring together with the nitrogen atom to which is bonded, in which case the alkylene chain or alkenylene chain may contain one or two oxygen atoms, sulfur atoms or nitrogen atoms, and a halogen atom, cyano, Nitro, C ₁ ~ C ₆ Alkyl, R ^15b Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, C ₁ ~ C ₆ Alkoxy, C ₁ ~ C ₆ Haloalkoxy, C ₁ ~ C ₆ Alkylthio, C ₁ ~ C ₆ Haloalkylthio, C ₁ ~ C ₆ Alkylsulfinyl, C ₁ ~ C ₆ Haloalkylsulfinyl, C ₁ ~ C ₆ Alkylsulfonyl, C ₁ ~ C ₆ Haloalkylsulfonyl, phenyl, (Z) _q Optionally substituted by a phenyl, oxo group or thioxo group substituted by
R ^14b Is a hydrogen atom, cyano, nitro, C ₁ ~ C ₆ Alkyl, R ^15d Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, C ₂ ~ C ₆ Alkenyl, R ^15d Optionally substituted with (C ₂ ~ C ₆ ) Alkenyl, C ₃ ~ C ₈ Cycloalkenyl, R ^15d Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkenyl, C ₂ ~ C ₆ Alkynyl, R ^15d Optionally substituted with (C ₂ ~ C ₆ ) Alkynyl, C ₃ ~ C ₈ Cycloalkyl, R ^15d Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkyl, -OR ^16d , -S (O) _r3 R ^16d , -C (O) OR ^16d , -C (O) SR ^16d , -C (S) OR ^16d , -C (S) SR ^16d , -C (O) R ^17d , -C (S) R ^17d , -C (O) N (R ^18d ) R ^19d , -C (S) N (R ^18d ) R ^19d , -S (O) _r3 N (R ^18d ) R ^19d , Phenyl, (Z) _q Phenyl, naphthyl, substituted by (Z) _q Naphthyl substituted by, D1-2, D1-7, D1-8, D1-10, D1-32, D1-33, D1-34, D1-36, D1-37, D1-38, D1-79, D1-80, D1-81, D1-82, D1-84, D1-85, D1-87, D1-92, D1-93, D1-95, D1-96 or D1-98 or R1- ^14b Is R ^13b Together with = C (R ^14e ) R ^14f May form,
R ^14e And R ^14f Each independently represents a hydrogen atom, cyano, nitro, C ₁ ~ C ₆ Alkyl, R ^15b Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, C ₂ ~ C ₆ Alkenyl, R ^15b Optionally substituted with (C ₂ ~ C ₆ ) Alkenyl, C ₃ ~ C ₈ Cycloalkenyl, R ^15b Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkenyl, C ₂ ~ C ₆ Alkynyl, R ^15b Optionally substituted with (C ₂ ~ C ₆ ) Alkynyl, C ₃ ~ C ₈ Cycloalkyl, R ^15b Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkyl, -OR ^16b , -S (O) _r3 R ^16b , -C (O) OR ^16b , -C (O) SR ^16b , -C (S) OR ^16b , -C (S) SR ^16b , -C (O) R ^17b , -C (S) R ^17b , -C (O) N (R ^18b ) R ^19b , -C (S) N (R ^18b ) R ^19b , -S (O) _r3 N (R ^18b ) R ^19b , Phenyl, (Z) _q Phenyl, naphthyl, substituted by (Z) _q Naphthyl substituted by, D1-2, D1-7, D1-8, D1-10, D1-32, D1-33, D1-34, D1-36, D1-37, D1-38, D1-79, D1-80, D1-81, D1-82, D1-84, D1-85, D1-87, D1-92, D1-93, D1-95, D1-96 or D1-98 or R1- ^14e Is R ^14f Together with C ₂ ~ C ₇ An alkylene chain or C ₂ ~ C ₇ By forming an alkenylene chain of R ^14e And R ^14f May form a 3- to 8-membered ring together with the carbon atom to which is bonded, in which case the alkylene chain or alkenylene chain may contain 1, 2 or 3 oxygen atoms, sulfur atoms or nitrogen atoms, and a halogen atom, Cyano, nitro, C ₁ ~ C ₆ Alkyl, R ^15b Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, C ₁ ~ C ₆ Alkoxy, C ₁ ~ C ₆ Haloalkoxy, C ₁ ~ C ₆ Alkylthio, C ₁ ~ C ₆ Haloalkylthio, C ₁ ~ C ₆ Alkylsulfinyl, C ₁ ~ C ₆ Haloalkylsulfinyl, C ₁ ~ C ₆ Alkylsulfonyl, C ₁ ~ C ₆ Haloalkylsulfonyl, phenyl, (Z) _q Optionally substituted by a phenyl, oxo group or thioxo group substituted by
R ^15a Is a halogen atom, cyano, nitro, C ₃ ~ C ₈ Cycloalkyl, C ₃ ~ C ₈ Halocycloalkyl, —OH, —OR ^16a , -SH, -S (O) _r2 R ^16a , -S (= NR ^18a ) R ^16a , -S (O) (= NR ^18a ) R ^16a , Phenyl, (Z) _q Phenyl, naphthyl, substituted by (Z) _q Naphthyl substituted by, D1-2, D1-7, D1-8, D1-10, D1-32, D1-33, D1-34, D1-36, D1-37, D1-38, D1-79, D1-80, D1-81, D1-82, D1-84, D1-85, D1-87, D1-92, D1-93, D1-95, D1-96, D1-98 or -Si (R ^40a ) (R ^40b ) R ⁴⁰ Represents
R ^15b Is a halogen atom, cyano, nitro, C ₃ ~ C ₈ Cycloalkyl, C ₃ ~ C ₈ Halocycloalkyl, —OH, —OR ^16b , -SH, -S (O) _r3 R ^16b , -S (= NR ^18b ) R ^16b , -S (O) (= NR ^18b ) R ^16b , -C (O) OH, -C (O) OR ^16b , -C (O) R ^17b , -C (O) N (R ^18b ) R ^19b , Phenyl, (Z) _q Phenyl, naphthyl, substituted by (Z) _q Naphthyl substituted by, D1-2, D1-7, D1-8, D1-10, D1-32, D1-33, D1-34, D1-36, D1-37, D1-38, D1-79, D1-80, D1-81, D1-82, D1-84, D1-85, D1-87, D1-92, D1-93, D1-95, D1-96, D1-98 or -Si (R ^40a ) (R ^40b ) R ⁴⁰ Represents
R ^15c Is a halogen atom, cyano, nitro, C ₃ ~ C ₈ Cycloalkyl, C ₃ ~ C ₈ Halocycloalkyl, —OH, —OR ^16c , -SH, -S (O) _r R ^16c , -S (= NR ^18c ) R ^16c , -S (O) (= NR ^18c ) R ^16c , Phenyl, (Z) _q Phenyl, naphthyl, substituted by (Z) _q Naphthyl substituted by, D1-2, D1-7, D1-8, D1-10, D1-32, D1-33, D1-34, D1-36, D1-37, D1-38, D1-79, D1-80, D1-81, D1-82, D1-84, D1-85, D1-87, D1-92, D1-93, D1-95, D1-96, D1-98 or -Si (R ^40a ) (R ^40b ) R ⁴⁰ Represents
R ^15d Is a halogen atom, cyano, nitro, C ₃ ~ C ₈ Cycloalkyl, C ₃ ~ C ₈ Halocycloalkyl, —OH, —OR ^16d , -SH, -S (O) _r3 R ^16d , -S (= NR ^18d ) R ^16d , -S (O) (= NR ^18d ) R ^16d , Phenyl, (Z) _q Phenyl, naphthyl, substituted by (Z) _q Naphthyl substituted by, D1-2, D1-7, D1-8, D1-10, D1-32, D1-33, D1-34, D1-36, D1-37, D1-38, D1-79, D1-80, D1-81, D1-82, D1-84, D1-85, D1-87, D1-92, D1-93, D1-95, D1-96, D1-98 or -Si (R ^40a ) (R ^40b ) R ⁴⁰ Represents
R ^16a , R ^16b And R ^16d Are each independently C ₁ ~ C ₆ Alkyl, C ₂ ~ C ₆ Alkenyl, C ₂ ~ C ₆ Alkynyl, C ₃ ~ C ₈ Cycloalkyl, C ₃ ~ C ₈ Cycloalkenyl, R ²⁰ Optionally substituted with (C ₁ ~ C ₆ ) Alkyl or -C (O) R ²² Represents
R ^16c Is cyano, C ₁ ~ C ₆ Alkyl, C ₂ ~ C ₆ Alkenyl, C ₂ ~ C ₆ Alkynyl, C ₃ ~ C ₈ Cycloalkyl, C ₃ ~ C ₈ Cycloalkenyl, R ²⁰ Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, R ²⁰ Optionally substituted with (C ₂ ~ C ₆ ) Alkenyl, R ²⁰ Optionally substituted with (C ₂ ~ C ₆ ) Alkynyl, R ²⁰ Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkyl, R ²⁰ Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkenyl, -S (O) _r R ²¹ , -C (O) R ²² , Phenyl, (Z) _q Phenyl, naphthyl, substituted by (Z) _q Naphthyl substituted by, D1-2, D1-7, D1-8, D1-10, D1-32, D1-33, D1-34, D1-36, D1-37, D1-38, D1-79, D1-80, D1-81, D1-82, D1-84, D1-85, D1-87, D1-92, D1-93, D1-95, D1-96 or D1-98,
R ^17a , R ^17b , R ^17c And R ^17d Are each independently a hydrogen atom, C ₁ ~ C ₆ Alkyl, C ₂ ~ C ₆ Alkenyl, C ₂ ~ C ₆ Alkynyl, C ₃ ~ C ₈ Cycloalkyl, C ₃ ~ C ₈ Cycloalkenyl, R ²⁰ Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, R ²⁰ Optionally substituted with (C ₂ ~ C ₆ ) Alkenyl, R ²⁰ Optionally substituted with (C ₂ ~ C ₆ ) Alkynyl, R ²⁰ Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkyl, R ²⁰ Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkenyl, phenyl, (Z) _q Phenyl, naphthyl, substituted by (Z) _q Naphthyl substituted by, D1-2, D1-7, D1-8, D1-10, D1-32, D1-33, D1-34, D1-36, D1-37, D1-38, D1-79, D1-80, D1-81, D1-82, D1-84, D1-85, D1-87, D1-92, D1-93, D1-95, D1-96 or D1-98,
R ^18a And R ^19a Each independently represents a hydrogen atom, cyano or C ₁ ~ C ₆ Represents alkyl,
R ^18b , R ^19b , R ^18d And R ^19d Are each independently a hydrogen atom, cyano, C ₁ ~ C ₆ Alkyl, C ₂ ~ C ₆ Alkenyl, C ₂ ~ C ₆ Alkynyl, C ₃ ~ C ₈ Cycloalkyl, C ₃ ~ C ₈ Cycloalkenyl, R ²⁰ Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, R ²⁰ Optionally substituted with (C ₂ ~ C ₆ ) Alkenyl, R ²⁰ Optionally substituted with (C ₂ ~ C ₆ ) Alkynyl, R ²⁰ Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkyl, R ²⁰ Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkenyl, phenyl, (Z) _q Phenyl, naphthyl, substituted by (Z) _q Naphthyl substituted by, D1-2, D1-7, D1-8, D1-10, D1-32, D1-33, D1-34, D1-36, D1-37, D1-38, D1-79, D1-80, D1-81, D1-82, D1-84, D1-85, D1-87, D1-92, D1-93, D1-95, D1-96 or D1-98 or R1- ^18b Is R ^19b Together with C ₂ ~ C ₇ An alkylene chain or C ₂ ~ C ₇ By forming an alkenylene chain of R ^18b And R ^19b May form a 3- to 8-membered ring together with the nitrogen atom to which is bonded, in which case the alkylene chain or alkenylene chain may contain one or two oxygen atoms, sulfur atoms or nitrogen atoms, and a halogen atom, cyano, Nitro, C ₁ ~ C ₆ Alkyl, R ²⁰ Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, C ₁ ~ C ₆ Alkoxy, C ₁ ~ C ₆ Haloalkoxy, C ₁ ~ C ₆ Alkylthio, C ₁ ~ C ₆ Haloalkylthio, C ₁ ~ C ₆ Alkylsulfinyl, C ₁ ~ C ₆ Haloalkylsulfinyl, C ₁ ~ C ₆ Alkylsulfonyl, C ₁ ~ C ₆ Haloalkylsulfonyl, phenyl, (Z) _q Optionally substituted by a phenyl, oxo group or thioxo group substituted by
R ^18c And R ^19c Are each independently a hydrogen atom, cyano, C ₁ ~ C ₆ Alkyl, R ²⁰ Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, -OR ²¹ , -S (O) _r R ²¹ , -C (O) OR ²¹ , -C (O) R ²² , -C (S) R ²² , Phenyl or (Z) _q Represents phenyl substituted by
R ²⁰ Is a halogen atom, cyano, nitro, C ₃ ~ C ₈ Cycloalkyl, C ₃ ~ C ₈ Cycloalkenyl, C ₁ ~ C ₆ Alkoxy, C ₁ ~ C ₆ Alkylthio, C ₁ ~ C ₆ Alkylsulfinyl, C ₁ ~ C ₆ Alkylsulfonyl, -C (O) OR ²¹ , Phenyl or (Z) _q Represents phenyl substituted by
R ²¹ And R ²² Are each independently C ₁ ~ C ₆ Alkyl, C ₁ ~ C ₆ Haloalkyl, phenyl or (Z) _q Represents phenyl substituted by
D1-2, D1-7, D1-8, D1-10, D1-32, D1-33, D1-34, D1-36, D1-37, D1-38, D1-51, D1-79, D1- 80, D1-81, D1-82, D1-84, D1-85, D1-87, D1-92, D1-93, D1-95, D1-96 and D1-98 are represented by the following structures, respectively. Represents the ring

X ¹ And X ^1b Are each independently a halogen atom, cyano, nitro, —OH, —SH, —NH ₂ , -CHO, -C (O) OH, -C (O) NH ₂ , -C (S) NH ₂ , -S (O) ₂ NH ₂ , C ₁ ~ C ₆ Alkyl, R ²⁸ Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, C ₂ ~ C ₆ Alkenyl, C ₂ ~ C ₆ Alkynyl, C ₃ ~ C ₈ Cycloalkyl, C ₂ ~ C ₆ Haloalkenyl, C ₂ ~ C ₆ Haloalkynyl, C ₃ ~ C ₈ Halocycloalkyl, C ₁ ~ C ₆ Alkoxy, C ₁ ~ C ₆ Haloalkoxy, C ₁ ~ C ₆ Alkylthio, C ₁ ~ C ₆ Haloalkylthio, C ₁ ~ C ₆ Alkylsulfinyl, C ₁ ~ C ₆ Haloalkylsulfinyl, C ₁ ~ C ₆ Alkylsulfonyl, C ₁ ~ C ₆ Haloalkylsulfonyl, C ₁ ~ C ₆ Alkylcarbonyl, C ₃ ~ C ₈ Cycloalkylcarbonyl, C ₁ ~ C ₆ Haloalkylcarbonyl, C ₃ ~ C ₈ Halocycloalkylcarbonyl, C ₁ ~ C ₆ Alkoxycarbonyl, C ₁ ~ C ₆ Haloalkoxycarbonyl, C ₁ ~ C ₆ Alkylaminosulfonyl, di (C ₁ ~ C ₆ Alkyl) aminosulfonyl, C ₁ ~ C ₆ Alkylaminocarbonyl, di (C ₁ ~ C ₆ Alkyl) aminocarbonyl, C ₁ ~ C ₆ Alkylamino or di (C ₁ ~ C ₆ Alkyl) amino, and when g1, g2 or g4 represents an integer of 2 or more, each X ¹ May be the same or different from each other, or when f4, f5, f7 or f9 represents an integer of 2 or more, each X ^1b May be the same as or different from each other, and two X ^1b Are substituted on the same carbon, two X ^1b Together oxo, thioxo, imino, C ₁ ~ C ₆ Alkylimino, C ₁ ~ C ₆ Alkoxyimino or C ₁ ~ C ₆ May form alkylidene,
X ^1a Is a hydrogen atom, cyano, -OH, -NH ₂ , -CHO, -C (O) NH ₂ , -C (S) NH ₂ , -S (O) ₂ NH ₂ , C ₁ ~ C ₆ Alkyl, C ₂ ~ C ₆ Alkenyl, C ₂ ~ C ₆ Alkynyl, C ₃ ~ C ₈ Cycloalkyl, R ²⁸ Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, R ²⁸ Optionally substituted with (C ₂ ~ C ₆ ) Alkenyl, R ²⁸ Optionally substituted with (C ₂ ~ C ₆ ) Alkynyl, R ²⁸ Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkyl, R ²⁸ Optionally substituted with (C ₃ ~ C ₈ ) Cycloalkenyl, C ₁ ~ C ₆ Alkoxy, C ₁ ~ C ₆ Haloalkoxy, C ₁ ~ C ₆ Alkylthio, C ₁ ~ C ₆ Alkylsulfinyl, C ₁ ~ C ₆ Alkylsulfonyl, C ₁ ~ C ₆ Haloalkylthio, C ₁ ~ C ₆ Haloalkylsulfinyl, C ₁ ~ C ₆ Haloalkylsulfonyl, C ₁ ~ C ₆ Alkylcarbonyl, C ₃ ~ C ₈ Cycloalkylcarbonyl, C ₁ ~ C ₆ Haloalkylcarbonyl, C ₃ ~ C ₈ Halocycloalkylcarbonyl, C ₁ ~ C ₆ Alkoxycarbonyl, C ₁ ~ C ₆ Haloalkoxycarbonyl, C ₁ ~ C ₆ Alkylaminosulfonyl, di (C ₁ ~ C ₆ Alkyl) aminosulfonyl, C ₁ ~ C ₆ Alkylaminocarbonyl, di (C ₁ ~ C ₆ Alkyl) aminocarbonyl, C ₁ ~ C ₆ Alkylamino, di (C ₁ ~ C ₆ Alkyl) amino, phenyl, C ₁ ~ C ₆ Represents phenyl optionally substituted with alkyl or phenyl optionally substituted with halogen atoms;
Z is a halogen atom, cyano, nitro, -OH, -SH, -NH ₂ , -CHO, -C (O) OH, -C (O) NH ₂ , -C (S) NH ₂ , -S (O) ₂ NH ₂ , C ₁ ~ C ₆ Alkyl, R ²⁸ Optionally substituted with (C ₁ ~ C ₆ ) Alkyl, C ₂ ~ C ₆ Alkenyl, C ₂ ~ C ₆ Alkynyl, C ₃ ~ C ₈ Cycloalkyl, C ₂ ~ C ₆ Haloalkenyl, C ₂ ~ C ₆ Haloalkynyl, C ₃ ~ C ₈ Halocycloalkyl, C ₁ ~ C ₆ Alkoxy, C ₁ ~ C ₆ Haloalkoxy, C ₁ ~ C ₆ Alkylthio, C ₁ ~ C ₆ Haloalkylthio, C ₁ ~ C ₆ Alkylsulfinyl, C ₁ ~ C ₆ Haloalkylsulfinyl, C ₁ ~ C ₆ Alkylsulfonyl, C ₁ ~ C ₆ Haloalkylsulfonyl, C ₁ ~ C ₆ Alkylcarbonyl, C ₃ ~ C ₈ Cycloalkylcarbonyl, C ₁ ~ C ₆ Haloalkylcarbonyl, C ₃ ~ C ₈ Halocycloalkylcarbonyl, C ₁ ~ C ₆ Alkoxycarbonyl, C ₁ ~ C ₆ Haloalkoxycarbonyl, C ₁ ~ C ₆ Alkylaminosulfonyl, di (C ₁ ~ C ₆ Alkyl) aminosulfonyl, C ₁ ~ C ₆ Alkylaminocarbonyl, di (C ₁ ~ C ₆ Alkyl) aminocarbonyl, C ₁ ~ C ₆ Alkylamino or di (C ₁ ~ C ₆ Alkyl) amino and when q represents an integer of 2 or more, each Z may be the same as or different from each other;
R ²⁸ And R ^28a Each independently represents a halogen atom, -OH, -SH, C ₁ ~ C ₆ Alkoxy, C ₁ ~ C ₆ Haloalkoxy, C ₁ ~ C ₆ Alkylthio, C ₁ ~ C ₆ Haloalkylthio, C ₁ ~ C ₆ Alkylsulfinyl, C ₁ ~ C ₆ Haloalkylsulfinyl, C ₁ ~ C ₆ Alkylsulfonyl or C ₁ ~ C ₆ Represents haloalkylsulfonyl,
R ⁴⁰ , R ^40a And R ^40b Are each independently C ₁ ~ C ₆ Represents alkyl,
g1 and n each independently represent an integer of 0, 1, 2, or 3;
g2 represents an integer of 0, 1 or 2;
g4 and f4 each independently represent an integer of 0, 1, 2, 3 or 4;
f5 represents an integer of 0, 1, 2, 3, 4 or 5,
f7 represents an integer of 0, 1, 2, 3, 4, 5, 6 or 7,
f9 represents an integer of 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9,
q represents an integer of 1, 2, 3, 4 or 5;
m1, m2 and m3 each independently represent an integer of 0 or 1,
r, r2 and r3 each independently represents an integer of 0, 1 or 2. ] The pyrazole derivative represented by these, or its salt. A ¹ represents -CR ¹
R ¹ , R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom or C ₁ -C ₆ alkyl;
The pyrazole derivative or a salt thereof according to claim ₁ , wherein R ² represents a halogen atom or C ₁ -C ₆ alkyl. A ¹ represents -N (-O) _m2 ,
R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom or C ₁ -C ₆ alkyl;
The pyrazole derivative or a salt thereof according to claim ₁ , wherein R ² represents a halogen atom or C ₁ -C ₆ alkyl. R ¹ represents a hydrogen atom or a halogen atom,
R ⁴ represents a hydrogen atom,
R ³ represents a hydrogen atom, a halogen atom or C ₁ -C ₆ alkyl,
R ^a is a hydrogen atom, C ₁ -C ₆ alkyl, (C ₁ -C ₆ ) alkyl optionally substituted with R ^5a , C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, -S (O) _r2 R ^6a, represents ^{-C (O) oR 6a, -C} (O) R 7a, -C (O) N (R 8a) R 9a or ^{-C (S) N (R 8a} ) R 9a,
R ^5a is cyano, C ₃ -C ₈ cycloalkyl, —OR ^11a , —S (O) _{r 2} R ^11a , —C (O) OH, —C (O) OR ^11a , —C (O) N (R ^13a ) represents R ^14a , phenyl, phenyl substituted by (Z) _q , D1-32, D1-33 or D1-34;
R ^6a represents C ₁ -C ₆ alkyl;
R ^7a represents C ₃ -C ₈ cycloalkyl, (C ₁ -C ₆ ) alkyl optionally substituted with R ^10a or —C (═NOR ^11a ) R ^12a ,
R ^8a represents a hydrogen atom or C ₁ -C ₆ alkyl;
R ^9a represents a hydrogen atom or C ₁ -C ₆ alkyl,
R ^10a represents —S (O) _r2 R ^11a ,
R ^11a is C ₁ -C ₆ alkyl, (C ₁ -C ₆ ) alkyl optionally substituted with R ^15a , C ₂ -C ₆ alkynyl, -C (O) OR ^16a , -C (O) R ^17a Or -C (O) N (R ^18a ) R ^19a
R ^11b represents C ₁ -C ₆ alkyl, (C ₁ -C ₆ ) alkyl optionally substituted with R ^15b , —C (O) OR ^16b or —C (O) R ^17b ,
R ^12a represents (C ₁ -C ₆ ) alkyl optionally substituted with R ^15a ,
R ^12b is a hydrogen atom, _cyano, C 1 -C ₆ ^alkyl, optionally substituted with ^{R 15c} _(C 1 ~C ₆₎ ^alkyl, optionally substituted with ^{R 15c} _(C 2 ~C ₆₎ alkenyl, optionally substituted with R ^15c _(C 3 ~C _{8) ^{cycloalkyl, -S (O) r R 16c}} , -C (O) R 17c, phenyl, phenyl substituted by _{(Z) q,} D1-2 , D1-32 or D1-34,
R ^13b is a hydrogen atom, C ₁ -C ₆ alkyl, (C ₁ -C ₆ ) alkyl optionally substituted with R ^15b , C ₂ -C ₆ alkenyl, —S (O) _r 3 R ^16b , —C ( O) OR ^16b , —C (O) R ^17b , —C (O) N (R ^18b ) R ^19b , phenyl or D1-37,
R ^14b represents a hydrogen atom,
R ^15a represents —OR ^16a , —S (O) _{r 2} R ^16a , phenyl or —Si (R ^40a ) (R ^40b ) R ⁴⁰ ,
R ^15b is a halogen atom, cyano, C ₃ -C ₈ cycloalkyl, —OR ^16b , —S (O) _r 3 R ^16b , —C (O) OR ^16b or —C (O) N (R ^18b ) R ^19b. Represents
R ^15c represents a halogen atom, —OR ^16c , —S (O) _r R ^16c or D 1-7;
R ^16a represents C ₁ -C ₆ alkyl or (C ₁ -C ₆ ) alkyl optionally substituted with R ²⁰ ;
R ^16b represents C ₁ -C ₆ alkyl or (C ₁ -C ₆ ) alkyl optionally substituted with R ²⁰ ;
R ^16c represents C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, (C ₁ -C ₆ ) alkyl optionally substituted with R ²⁰ , —S (O) _r R ²¹ or D1-32,
R ^17a represents C ₁ -C ₆ alkyl or phenyl;
R ^17b represents a hydrogen atom, C ₁ -C ₆ alkyl, C ₃ -C ₈ cycloalkyl or (C ₁ -C ₆ ) alkyl optionally substituted with R ²⁰ ,
R ^17c represents C ₁ -C ₆ alkyl;
R ^18a and R ^19a each independently represent C ₁ -C ₆ alkyl;
R ^18b represents a hydrogen atom or phenyl substituted by (Z) _q ;
R ^19b represents a hydrogen atom or (C ₁ -C ₆ ) alkyl optionally substituted with R ²⁰ ,
R ²⁰ represents a halogen atom, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio or phenyl,
R ²¹ represents phenyl substituted by (Z) _q ;
X ¹ represents (C ₁ -C ₆ ) alkyl optionally substituted with R ²⁸ ,
R ²⁸ represents a halogen atom,
Z represents a halogen atom or a _C 1 -C ₆ alkyl,
g1 and g4 each independently represent an integer of 0 or 1,
m1, m3 and n represent 0;
q represents an integer of 1 or 2,
r and r3 each independently represents an integer of 0, 1 or 2;
The pyrazole derivative or a salt thereof according to claim 2, wherein r2 represents 0 or an integer of 2.   The pest control agent which contains the 1 type (s) or 2 or more types chosen from the pyrazole derivative and its salt of Claims 1-4 as an active ingredient.   An agrochemical containing one or more selected from the pyrazole derivative according to claim 1 and a salt thereof as an active ingredient.   A mammal or avian internal or ectoparasite control agent comprising one or more selected from the pyrazole derivatives and salts thereof according to claim 1 as active ingredients.   An insecticide or acaricide containing, as an active ingredient, one or more selected from the pyrazole derivatives and salts thereof according to claim 1.   The soil treatment agent which contains the 1 type (s) or 2 or more types chosen from the pyrazole derivative and its salt of Claims 1-4 as an active ingredient.   The soil treatment agent according to claim 9, wherein the soil treatment method is soil irrigation treatment.