JP2013241403A - Malonic acid amide compound and pest control agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel pest control agent with low toxicity and low persistence, especially an insecticide or an acaricide.SOLUTION: A malonic acid amide compound represented by general formula (1) and a pest control agent are disclosed (wherein, Q represents a heterocyclic ring of Q-1 or Q-2, Rrepresents a 1-6C alkyl group arbitrarily substituted by R, each of Rand Rindependently represents a hydrogen atom, a 1-6C alkyl group, a 1-6C alkyl group arbitrarily substituted by R, a 3-6C cycloalkenyl group, or a ring of U-1 to U-10, Rrepresents -CHO, -C(O)OH, -C(O)R, -C(O)OR, -C(O)N(R)Ror -S(O)mR, Rrepresents T-1 to T-26, Rrepresents a ring of U-1 to U-10, and Rrepresents a 1-6C alkyl group or the like).

Description

  The present invention relates to a novel malonic acid amide compound and a salt thereof, and a pest control agent comprising 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, Patent Documents 1 and 2 disclose malonic acid amide compounds, but none of the malonic acid amide compounds according to the present invention are disclosed. 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.

International Publication No. 2009/099929 International Publication No. 2011/017351

  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 research aimed at solving the above problems, the present inventors have found that the novel malonamide compound represented by the following formula (1) according to the present invention has excellent pest control activity, particularly insecticide The present invention was completed by discovering that it is an extremely useful compound exhibiting acaricidal activity.

  That is, the present invention relates to the following [1] to [12].

[1]
Formula (1):

[Wherein Q represents an aromatic heterocycle represented by either Q-1 or Q-2,

R ¹ represents a C ₁ -C ₆ alkyl group optionally substituted by R ⁸ ;
R ² and ^{R 3} are each independently a hydrogen _atom, C 1 -C ₆ alkyl ^group, _C 1 -C ₆ alkyl group optionally substituted by ^{R _12,} C 3 -C ₆ cycloalkyl ^group, the ^{R 12} optionally substituted _C 3 -C ₆ cycloalkyl _group, C 2 -C ₆ alkenyl ^group, _C 2 -C ₆ alkenyl group optionally substituted by ^{R _12,} C 3 -C ₆ cycloalkenyl ^group, the ^{R 12} It represents a ring represented by any one of C ₃ -C ₆ cycloalkenyl group, or U-10 from U-1 optionally substituted,
R ⁴ is a cyano group, —CHO, —C (O) OH, —C (O) R ²⁴ , —C (O) OR ²⁴ , —C (O) SR ²⁴ , —C (O) N (R ²⁵ ) R ²⁶ , —S (O) mR ²⁴ or —P (O) (OR ²⁷ ) OR ²⁸ ;
W is a halogen _atom, C 1 -C ₆ alkyl group, a _C 1 -C ₆ alkyl group, or -OR ^6, optionally substituted by ^{R 5,} when p1 and p2 represents an integer of 2 or more, each of the W may be the same as or different from each other;
R ⁵ represents a halogen atom,
R ⁶ _represents a _C 1 -C ₆ alkyl group optionally substituted by C 1 -C ₆ alkyl group or ^{R 7,}
R ⁷ represents a halogen atom,
R ⁸ represents a ring represented by any of T-1 to T-26,
T-1 to T-26 each represent a ring represented by the following structural formula;

X is a halogen _atom, C 1 -C ₆ alkyl group, a _C 1 -C ₆ alkyl or ^{OR 10} optionally substituted by ^{R 9,} when q1, q2, q3 or q4 is an integer of 2 or more Each X may be the same as or different from each other;
R ⁹ represents a halogen atom,
R ¹⁰ _represents a _C 1 -C ₆ alkyl group optionally substituted by C 1 -C ₆ alkyl group or ^{R 11,}
R ¹¹ represents a halogen atom,
R ¹² represents a halogen atom, OR ¹³ , U-1 to U-9 or U-10,
R ¹³ _represents a _C 1 -C ₆ alkyl group optionally substituted by C 1 -C ₆ alkyl group or ^{R 14,}
R ¹⁴ represents a halogen atom,
U-1 to U-10 each represent a ring represented by the following structural formula,

Z is a cyano group, a nitro group, a hydroxyl group, a halogen _atom, C 1 -C ₆ alkyl ^group, _C 1 -C ₆ alkyl group optionally substituted by ^{R _15,} C 3 -C ₆ cycloalkyl ^group, the ^{R 15} optionally substituted cycloalkyl _group, C 2 -C ₆ alkenyl ^group, _C 2 -C ₆ alkenyl group optionally substituted by ^{R _15,} C 3 -C ₆ cycloalkenyl ^group, optionally substituted by ^{R 15} C ₃ -C ₆ cycloalkenyl _group, C 2 -C ₆ alkynyl group, V-1~V-6, -CHO , -C (O) R 16, -C (O) OH, -C (O) OR 16 ^{, -C (O) N (R} 17) R 18, -OR 16, -OC (O) R 16, -OC (O) OR 16, -OS (O) nR 16, -S (O) mR 16, ^{-N (R 17) R 18,} -SF 5 , or -C = Represents ^{R 31) R 32, r1,} r2, r3, when r4 or r5 is an integer of 2 or more, each Z may be the even or different from each other the same as each other,
Za represents a hydrogen _atom, C 1 -C ₆ alkyl ^group, _C 1 -C ₆ alkyl group, V-1 to V-3 or V-4 optionally substituted by ^{R 15,}
R ¹⁵ represents a halogen atom or -OR ¹⁹ ;
R ¹⁶ _represents a C 1 -C ₆ alkyl ^group, _C 1 -C ₆ alkyl group or a phenyl group optionally substituted by ^{R 20,}
Or R ¹⁷ and ^{R 18} each independently represent a hydrogen _atom, C 1 -C ₆ alkyl or _C 1 -C ₆ alkyl group optionally substituted by ^{R 20, or} together with ^{R 17} is ^{R 18} is in the C by ₂ -C ₆ to form an alkylene or C ₂ -C ₆ alkenylene chain, it indicates that may form a 3- to 7-membered ring together with the nitrogen atom to which they are attached,
R ¹⁹ represents a C ₁ -C ₆ alkyl group,
R ²⁰ represents a halogen atom or —OR ²¹ ;
R ²¹ represents a C ₁ -C ₆ alkyl group,
V-1 to V-6 each represent a ring represented by the following structural formula;

E is a cyano group, a halogen _atom, C 1 -C ₆ alkyl ^group, _C 1 -C ₆ alkyl group optionally substituted by ^{R _33,} C 3 -C ₆ cycloalkyl ^group, optionally substituted by ^{R 33} C _{3 to} C ₆ cycloalkyl group, —OR ²² or —S (O) mR ^35, and when t1, t2 or t3 represents an integer of 2 or more, each E may be the same as or different from each other. May be different,
R ²² _represents a _C 1 -C ₆ alkyl group optionally substituted by C 1 -C ₆ alkyl group or ^{R 23,}
R ²³ represents a halogen atom,
R ²⁴ _represents a C 1 -C ₆ alkyl ^group, _C 1 -C ₆ alkyl group or a phenyl group optionally substituted by ^{R 29,}
Or R ²⁵ and ^{R 26} each independently represent a hydrogen _atom, C 1 -C ₆ alkyl or _C 1 -C ₆ alkyl group optionally substituted by ^{R 29, or, R 25} is combined with ^{R 26} is in the C by ₂ -C ₆ to form an alkylene or C ₂ -C ₆ alkenylene chain, it indicates that may form a 3- to 7-membered ring together with the nitrogen atom to which they are attached,
R ²⁷ and ^{R 28} are each independently hydrogen _atom, C 1 -C ₆ alkyl ^group, or represents a _C 1 -C ₆ alkyl group optionally substituted by ^{R 29, or} together with ^{R 27} is ^{R 28} is in the C by ₂ -C ₆ to form an alkylene or C ₂ -C ₆ alkenylene chain, it indicates that may form a 5-9 membered ring together with the oxygen atom attached,
R ²⁹ represents a halogen atom or —OR ³⁰ ;
R ³⁰ represents a C ₁ -C ₆ alkyl group,
R ³¹ represents -NR ³⁶ ;
R ³² represents a C ₁ -C ₆ alkyl group or —NR ³⁷ R ³⁸ ,
R ³³ represents a halogen atom,
R ³⁴ _represents a _C 1 -C ₆ alkyl group optionally substituted by C 1 -C ₆ alkyl group or ^{R 39,}
R ³⁶ represents a hydrogen atom or OR ⁴⁰ ,
R ³⁷ and ^{R 38} are each independently hydrogen _atom, C 1 -C ₆ alkyl ^group, _C 1 -C ₆ alkyl group optionally substituted by ^{R 42, -OR 43, -C (} O) R 45, —OC (O) R ⁴⁶ or a phenyl group, or R ³⁷ together with R ³⁸ forms a C ₂ -C ₆ alkylene chain or a C ₂ -C ₆ alkenylene chain to bind nitrogen Represents that a 3- to 7-membered ring may be formed together with the atoms;
R ³⁹ represents a halogen atom,
R ⁴⁰ represents a hydrogen _{atom, C} 1 -C ₆ alkyl group optionally substituted by C 1 -C ₆ alkyl group or ^{R 41,}
R ⁴¹ represents a halogen atom,
R ⁴² represents a halogen atom or a phenyl group,
R ⁴³ represents a hydrogen _atom, C 1 -C ₆ alkyl ^group, _C 1 -C ₆ alkyl group optionally substituted by ^{R _44,} a C 2 -C ₆ alkenyl group or _C 2 -C ₆ alkynyl group,
R ⁴⁴ represents a halogen atom,
R ⁴⁵ represents a C ₁ -C ₆ alkyl group,
R ⁴⁶ represents a C ₁ -C ₆ alkyl group or a C ₃ -C ₆ cycloalkyl group,
p1 represents an integer of 0, 1, 2, 3 or 4;
p2 represents an integer of 0, 1 or 2;
q1 represents an integer of 0, 1, 2, 3 or 4;
q2 represents an integer of 0, 1 or 2,
q3 represents an integer of 0, 1, 2, 3, 4, 5, 6 or 7,
q4 represents an integer of 0, 1, 2, or 3,
q5 represents an integer of 0 or 1,
r1 represents an integer of 0, 1, 2, 3, 4 or 5;
r2 represents an integer of 0, 1, 2, 3 or 4; r3 represents an integer of 0, 1, 2, or 3;
r4 represents an integer of 0, 1 or 2,
r5 represents an integer of 0, 1, 2, 3, 4 or 5;
m represents an integer of 0, 1 or 2;
n represents an integer of 1 or 2,
t1 represents an integer of 0, 1, 2, 3, 4 or 5;
t2 represents an integer of 0, 1, 2, 3 or 4;
t3 represents an integer of 0, 1, 2, or 3. ] The malonamide compound represented by these, or its salt. However, the compound represented by Formula (2) is excluded.

[2]
R ² is a hydrogen _atom, C 1 -C ₆ alkyl ^group, _C 1 -C ₆ alkyl group optionally substituted by ^{R _12,} C 3 _{~C 6} cycloalkyl group, U-1, U-2, or U- 10
R ³ represents a hydrogen atom or a C ₁ -C ₆ alkyl group,
R ⁴ is —C (O) OH, —C (O) R ²⁴ , —C (O) OR ²⁴ , —C (O) SR ²⁴ , —C (O) N (R ²⁵ ) R ²⁶ , —S. (O) represents mR ²⁴ or -P (O) (OR ²⁷ ) OR ²⁸ ;
W represents a halogen atom or a _C 1 -C ₆ alkyl group,
R ⁸ represents a ring represented by any of T-1 to T-3 or T-4,
X represents a C ₁ -C ₆ alkyl group optionally substituted with a halogen atom or R ⁹ ;
R ¹² represents a ring represented by either U-1 or U-3,
Z is a nitro group, a hydroxyl group, a halogen _atom, C 1 -C ₆ alkyl ^group, _C 1 -C ₆ alkyl group optionally substituted by ^{R 15, V-3, V} -5, -OR 16, -OC ( ^{O) R 16, -OS (O} ) nR 16, -S (O) mR 16 or ^-N (R ¹⁷⁾ represents an ^{R 18,}
R ¹⁵ represents a halogen atom,
R ¹⁷ and R ¹⁸ each independently represent a C ₁ -C ₆ alkyl group,
E represents a halogen atom or —OR ²² ;
R ²² represents a C ₁ -C ₆ alkyl group,
R ²⁴ represents a C ₁ -C ₆ alkyl group or a phenyl group,
R ²⁵ represents a hydrogen atom or a C ₁ -C ₆ alkyl group,
R ²⁶ _is, represent a _C 1 -C ₆ alkyl group optionally substituted by C 1 -C ₆ alkyl group or ^{R 29, or, R 25} is _C 2 -C ₆ alkylene chain together with ^{R 26} Represents that a 3- to 7-membered ring may be formed together with the nitrogen atom to be bonded,
R ²⁷ and R ²⁸ each independently represent a C ₁ -C ₆ alkyl group,
R ²⁹ represents a halogen atom,
p1 represents an integer of 0 or 1,
p2 represents an integer of 0 or 1,
q1 represents an integer of 1,
q2 represents an integer of 1,
q3 represents an integer of 0;
q4 represents an integer of 0;
r1 represents an integer of 0, 1 or 2;
r2 represents an integer of 1 or 2, r5 represents an integer of 0,
t2 represents an integer of 1,
t3 is a malonamide compound or a salt thereof according to the above [1], wherein the integer represents 0.

[3]
Q represents an aromatic heterocycle represented by Q-1.
R ² represents a C ₁ -C ₆ alkyl group or U-1 optionally substituted with R ¹² ,
R ³ represents a hydrogen atom,
R ⁴ represents —C (O) OH, —C (O) OR ²⁴ or —C (O) SR ²⁴ ;
R ¹² represents a ring represented by U-1,
Z represents a halogen _atom, C 1 -C ₆ alkyl ^group, a _C 1 -C ₆ alkyl group or ^{-OR 16} and optionally substituted by ^{R 15,}
R ¹⁶ represents a C ₁ -C ₆ alkyl group,
R ²⁴ represents a C ₁ -C ₆ alkyl group,
The malonic acid amide compound or a salt thereof according to [2] above, wherein p1 represents an integer of 0.

[4]
Formula (3):

[Wherein Q represents an aromatic heterocycle represented by either Q-1 or Q-2,
R ¹ represents a C ₁ -C ₆ alkyl group optionally substituted by R ⁸ ;
R ² represents U-1,
R ³ represents a hydrogen atom or a C ₁ -C ₆ alkyl group,
W represents a halogen atom or a _C 1 -C ₆ alkyl group,
R ⁸ represents T-1 to T-3 or T-4,
X represents a C ₁ -C ₆ alkyl group optionally substituted with a halogen atom or R ⁹ ;
R ⁹ represents a halogen atom,
Z is a nitro group, a hydroxyl group, a halogen _atom, C 1 -C ₆ alkyl ^group, _C 1 -C ₆ alkyl group optionally substituted by ^{R 15, V-3, V} -5, -OR 16, -OC ( ^{O) R 16, -OS (O} ) nR 16, -S (O) mR 16 or ^-N (R ¹⁷⁾ represents an ^{R 18,}
R ¹⁵ represents a halogen atom,
R ¹⁶ _represents a C 1 -C ₆ alkyl ^group, _C 1 -C ₆ alkyl group or a phenyl group optionally substituted by ^{R 20,}
R ¹⁷ and R ¹⁸ each independently represent a C ₁ -C ₆ alkyl group,
R ²⁰ represents a halogen atom or OR ²¹ ;
R ²¹ represents a C ₁ -C ₆ alkyl group,
E represents a halogen atom or —OR ²² ;
R ²² represents a C ₁ -C ₆ alkyl group,
p1 represents an integer of 0 or 1,
p2 represents an integer of 0 or 1,
q1 represents an integer of 1,
q2 represents an integer of 1,
q3 represents an integer of 0;
q4 represents an integer of 0;
r1 represents an integer of 1 or 2,
m represents an integer of 0, 1 or 2;
n represents an integer of 0, 1 or 2;
t2 represents an integer of 1,
t3 represents an integer of 0. Or a salt thereof.

[5]
Q represents an aromatic heterocycle represented by Q-1.
R ³ represents a hydrogen atom,
W _represents a C 1 -C ₆ alkyl group,
R ⁸ represents T-1, T-2 or T-4,
X represents a halogen atom,
Z represents a halogen _atom, C 1 -C ₆ alkyl ^group, _C 1 -C ₆ alkyl group optionally substituted by ^{R 15,} V-3, the ^{-OR 16} or -S (O) ^{mR 16,}
R ¹⁶ _represents a _C 1 -C ₆ alkyl group optionally substituted by C 1 -C ₆ alkyl group or ^{R 20,}
R ²⁰ represents a halogen atom,
E represents a halogen atom;
m is a phenylacetamide compound or a salt thereof according to the above [4], wherein 0 represents an integer of 0 or 2.
[6]
An agrochemical containing, as an active ingredient, one or more selected from the malonic acid amide compounds and salts thereof according to the above [1] to [5].
[7]
A mammal or bird internal or ectoparasite control agent containing one or more malonamide compounds and salts thereof described in [1] to [5] as active ingredients.
[8]
An insecticide or acaricide containing, as an active ingredient, one or more selected from the malonic acid amide compounds and salts thereof described in [1] to [5] above.
[9]
The seed treatment agent which contains 1 type, or 2 or more types chosen from the malonic acid amide compound of the said [1]-[5], and those salts as an active ingredient.
[10]
The seed treatment agent according to [9] above, wherein the seed treatment method is immersion treatment.
[11]
A soil treatment agent containing, as an active ingredient, one or more selected from the malonic acid amide compounds according to the above [1] to [5] and salts thereof.
[12]
The soil treatment agent according to the above [11], 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. 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.

  The compounds encompassed by the present invention may have threo-isomers and erythro-isomers depending on the type of the substituent, and the present invention includes these threo-isomers, erythro-isomers or threo-isomers and Includes mixtures containing erythro-forms in any proportion.

  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 a salt according to a conventional method are, for example, hydrohalic acid salts such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, Salts of inorganic acids such as 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, 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 and other carboxylic acid salts, glutamic acid, Salts of amino acids such as aspartic acid, alkali metal salts such as lithium, sodium and potassium, alkalis such as calcium, barium and magnesium Earth metal salts, aluminum salts, tetramethylammonium salts, tetrabutylammonium salts, may be quaternary ammonium salts such as benzyltrimethylammonium salts.

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

  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 Ca to Cb alkyl in the present specification represents a linear or branched hydrocarbon group having a to b carbon atoms, for example, methyl group, ethyl group, n-propyl group, i- Specific examples include propyl group, n-butyl group, i-butyl group, s-butyl group, tert-butyl group, n-pentyl group, 1,1-dimethylpropyl group, n-hexyl group, etc. Selected within the specified number of carbon atoms.

  The notation of Ca to Cb cycloalkyl in the present specification represents a cyclic hydrocarbon group having a to b carbon atoms and forms a monocyclic or complex ring structure from 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.

  The notation of Ca to Cb alkenyl in the present specification is an unsaturated carbonization having a linear or branched chain composed of a to b carbon atoms and having one or more double bonds in the molecule. Represents a hydrogen 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 -A dimethyl-2- propenyl group etc. are mentioned as a specific example, and it selects in the range of each designated number of carbon atoms.

  The notation of Ca to Cb cycloalkenyl in the present specification represents a cyclic unsaturated hydrocarbon group having 1 to 2 or more double bonds, and is a three-membered ring. To 6-membered monocyclic or complex ring structures 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 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, (R ¹⁷ together with R ¹⁸ forms a C _a -C _b alkylene chain or a C _a -C _b alkenylene chain, thereby forming a _3- to 7-membered ring together with the nitrogen atom to be bonded. Or the like, R ¹⁷ and R ¹⁸ are bonded together to form an alkylene chain having a carbon number of a to b or an alkenylene chain having a carbon number of a to b. A 3- to 6-membered ring may be formed together with the nitrogen atom to be formed, and the formed ring may be optionally substituted with an alkyl group within the range of the specified number of carbon atoms. Specific examples include aziridine, azetidine, pyrrolidine, 3-methylpyrrolidine, piperidine, 2,5-dihydro-1H-pyrrole, 1,2,3,6-tetrahydropyridine, etc., each having the designated number of carbon atoms. The range is selected.

^{(R 27} herein may form a 5-9 membered ring together with the oxygen atom which together with ^{R 28} forms a _C a -C _b alkylene chain or _C a -C _b alkenylene chain, binds ), R ²⁷ and R ²⁸ are combined to form an alkylene chain having a carbon number of a to b or an alkenylene chain having a carbon number of a to b, thereby binding oxygen atoms. And a 5- to 9-membered ring may be formed, and the formed ring may be optionally substituted with an alkyl group within the range of the specified number of carbon atoms. Preferred ring members include 5-membered rings or 6-membered rings, and specific examples include, for example, substituents represented by the following structures, and are selected within the range of each designated number of carbon atoms.

Optionally substituted by ^{R 5} in this specification _(C a _{~C b)} alkyl, optionally substituted by ^{R 7} _(C a _{~C b)} alkyl, optionally substituted by ^{R 8} _(C a ~ C _b) alkyl, optionally substituted by ^{R 9} _(C a ^~C _b) ^alkyl, optionally substituted by ^{R 11} _(C a ^~C _b) ^alkyl, optionally substituted by ^{R 12} _{(C a} -C _b) ^alkyl, optionally substituted by ^{R 14} _(C a ~C _b) ^alkyl, optionally substituted by ^{R 15} _(C a ~C _b) ^alkyl, optionally substituted by ^{R 20} (C _a -C _b) ^alkyl, optionally substituted by ^{R 23} _(C a ~C _b) ^alkyl, optionally substituted by ^{R 29} _(C a ~C _b) is substituted ^alkyl, optionally by ^{R 33} And _(C a _{~C b)} substituted ^alkyl, optionally substituted by ^{R 39} _(C a _{~C b)} ^alkyl, optionally substituted by ^{R 41} _(C a _{~C b)} ^alkyl, optionally by ^{R 42} been _(C a _{~C b)} alkyl or optionally substituted by ^{R 44} _(C a _{~C b)} notation alkyl or the like, any of ^{R 5, R 7, R 8} , R 9, R 11, R ¹² , R ¹⁴ , R ¹⁵ , R ²⁰ , R ²³ , R ²⁹ , R ³³ , R ³⁹ , R ⁴¹ , R ⁴² or R ⁴⁴ , the number of carbon atoms in which hydrogen atoms bonded to carbon atoms are optionally substituted It represents an alkyl group having the above-mentioned meanings consisting of a to b, and is selected within the range of each designated number of carbon atoms. At this time, the substituents R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ²⁰ , R ²³ , R ²⁹ on each (C _a -C _b ) alkyl group. , R ³³ , R ³⁹ , R ⁴¹ , R ⁴² or R ⁴⁴ , each R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ²⁰ , R ²³ , R ²⁹ , R ³³ , R ³⁹ , R ⁴¹ , R ⁴² or R ⁴⁴ may be the same as or different from each other.

Optionally substituted by ^{R 12} herein _(C a _{~C b)} ^cycloalkyl, optionally substituted by ^{R 15} _(C a _{~C b)} optionally substituted by cycloalkyl or ^{R 33} (C _{a to} C _b ) Cycloalkyl and the like are as defined above, wherein the number of carbon atoms in which a hydrogen atom bonded to a carbon atom is optionally substituted by any R ¹² , R ¹⁵ or R ³³ is _a to _b. And is selected in the range of each designated number of carbon atoms. At this time, when there are two or more substituents R ¹² , R ¹⁵ or R ³³ on each (C _a -C _b ) cycloalkyl group, each R ¹² , R ¹⁵ or R ³³ is the same as or different from each other. Further, the substitution position may be a ring structure part, a side chain part, or both.

Notation _(C a _{~C b)} alkenyl or the like which is optionally substituted by optionally substituted _(C a _{~C b)} alkenyl or ^{R 15} by ^{R 12} herein, by any ^{R 12} or ^{R 15} Represents an alkenyl group having the above-mentioned meaning, wherein the number of carbon atoms is optionally substituted with hydrogen atoms bonded to carbon atoms, and is selected within the range of the respective designated number of carbon atoms. At this time, when two or more substituents R ¹² or R ¹⁵ on each (C _a -C _b ) alkenyl group are present, each R ¹² or R ¹⁵ may be the same as or different from each other.

Optionally substituted with R ¹² _(C a ~C _b) by cycloalkenyl or optionally substituted with ^{R 15} _(C a ^~C _b) notation cycloalkenyl, any ^{R 12} or ^{R 15,} carbon atoms Represents a cycloalkenyl group having the above-mentioned meaning, wherein the number of carbon atoms arbitrarily substituted with hydrogen atoms bonded to is selected from a range of each designated number of carbon atoms. At this time, when two or more substituents R ¹² or R ¹⁵ on each (C _a -C _b ) cycloalkenyl group are present, each R ¹² or R ¹⁵ may be the same as or different from each other, and further substituted The position may be a ring structure moiety, a side chain moiety, or both.

  Next, the manufacturing method of this invention compound is demonstrated.

  The malonamide compound represented by the formula (1) can be produced, for example, by the following method.

  Manufacturing method A

Formula (4) [wherein Q and R ¹ represent the same meaning as described above. And a compound represented by formula (5) [wherein R ² , R ³ and R ⁴ represent the same meaning as described above. ] By reacting the compound represented by formula (1) [wherein Q, R ¹ , R ² , R ³ and R ⁴ represent the same meaning as described above. This invention compound represented by this can be manufactured.

  In this reaction, the compound represented by the formula (5) can be used in the range of 0.5 to 100 equivalents with respect to 1 equivalent of the compound represented by the formula (4).

  Examples of the condensing agent used include 1H-benzotriazol-1-yloxytris (dimethylamino) phosphonium hexafluorophosphate, N, N′-dicyclohexylcarbodiimide, 1- (3-dimethylaminopropyl) -3- Examples thereof include ethyl carbodiimide hydrochloride, 2-chloro-1-methylpyridinium iodide and the like, and can be used in the range of 0.5 to 50 equivalents with respect to 1 equivalent of the compound represented by formula (5).

  When a base is used, as the base to be used, an organic base such as triethylamine, pyridine, 4- (dimethylamino) pyridine, or an inorganic base such as potassium carbonate or sodium carbonate can be used if necessary. Can be used in the range of 0.1 to 50 equivalents relative to 1 equivalent of the compound represented by formula (1).

  When using a solvent, examples of the solvent used include N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolinone, water and other polar solvents, methanol , Alcohols such as ethanol, propanol, 2-propanol, ethylene glycol, ethers such as diethyl ether, tetrahydrofuran, diphenyl ether, aromatic hydrocarbons such as benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, 1 Halogenated hydrocarbons such as 1,2-dichloroethane, 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 (4) are known compounds, and others can be synthesized according to known methods described in the literature. For example, it can be prepared according to the method described in (Journal of Organic Chemistry 2010, 75, 2206, International Publication No. 2009/099929).

  Some of the compounds represented by the formula (5) are known compounds, and others are described in the literature (for example, Organic Letters 2007, Vol. 9, p. 3469, International Publication No. 2011/100838, Bioorganic And Medicinal Chemistry Letters 2011, Vol. 21, p. 1832).

  Manufacturing method B

The compound represented by the formula (4) and the formula (6) [wherein R ² , R ³ and R ⁴ have the same meaning as described above, and Xa represents a leaving group such as a halogen atom. The compound of the present invention represented by the formula (1) can be produced by reacting the compound represented by formula (1) with a solvent if necessary and with a base if necessary.

  In this reaction, the compound represented by the formula (6) can be used in the range of 0.5 to 100 equivalents with respect to 1 equivalent of the compound represented by the formula (4).

  When a base is used, examples of the base used include organic bases such as triethylamine, pyridine, 4- (dimethylamino) pyridine, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, potassium hydroxide, sodium hydroxide. Inorganic bases such as sodium hydride and the like, and can be used in the range of 0.1 to 50 equivalents relative to 1 equivalent of the compound represented by the formula (4).

  When using a solvent, examples of the solvent used include N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolinone, water and other polar solvents, methanol , Alcohols such as ethanol, propanol, 2-propanol, ethylene glycol, ethers such as diethyl ether, tetrahydrofuran, diphenyl ether, aromatic hydrocarbons such as benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, 1 Halogenated hydrocarbons such as 1,2-dichloroethane, 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 the formula (6) are known compounds, and others are described in the literature (for example, Journal of Organics) from the compound represented by the formula (5) represented by the production method A. Chemistry 1992, 57, 3463).

  Manufacturing method C

Among the compounds of the present invention, R ⁴ is —C (O) OR ^4a (R ^4a represents a C _{1 to} C ₆ alkyl group, etc.) and a compound represented by the formula (1) a; [Wherein, R ^4b represents —OR ²⁴ or —N (R ²⁵ ) R ²⁶ , R ²⁴ , R ²⁵ and R ²⁶ represent the same meaning as described above, and M represents a hydrogen atom, lithium, sodium, potassium An alkali metal salt such as calcium, barium or magnesium, or an alkaline earth metal salt. The compound of the present invention represented by the formula (1) b can be produced by reacting the compound represented by formula (1) b with a solvent if necessary and a base if necessary.

  In this reaction, the compound represented by the formula (7) can be used in the range of 0.5 to 100 equivalents with respect to 1 equivalent of the compound represented by the formula (1) a.

  When M is a hydrogen atom, a compound of the present invention represented by formula (1) b is produced by reacting a compound represented by formula (1) a with a compound represented by formula (7) using a base. can do.

  When a base is used, examples of the base used include sodium hydride, n-butyllithium, potassium carbonate, triethylamine, pyridine, 4- (dimethylamino) pyridine and the like, and a compound represented by the formula (7) It can be used in the range of 0.1 to 50 equivalents per equivalent.

  In the case of using a solvent, examples of the solvent used include N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolinone, water and other polar solvents, methanol, Alcohols such as ethanol, propanol, 2-propanol and ethylene glycol, ethers such as diethyl ether, tetrahydrofuran and diphenyl ether, aromatic hydrocarbons such as benzene, toluene and xylene, halogens such as methylene chloride, chloroform and carbon tetrachloride And aliphatic hydrocarbons such as pentahydrocarbons, 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 (7) are known compounds, and some of them are commercially available.

  Manufacturing method D

Among the compounds of the present invention, a compound represented by formula (1) c wherein R ³ is a hydrogen atom, and formula (8) [wherein R ³ represents the same meaning as described above, Xb represents a halogen atom, alkylcarbonyloxy Group (for example, acetyloxy group and the like), arylcarbonyloxy (for example, benzoyl group and the like), alkylsulfonyloxy (for example, methanesulfonyloxy group and the like), haloalkylsulfonyloxy (for example, trifluoromethanesulfonyloxy group and the like), arylsulfonyl Oxy (for example, 4-methylphenylsulfonyloxy group etc.) etc. are represented. The compound of the present invention represented by the formula (1) can be produced by reacting the compound represented by the formula (1) with a solvent if necessary and with a base if necessary.

  In this reaction, the compound represented by the formula (8) can be used in the range of 0.5 to 50 equivalents with respect to 1 equivalent of the compound represented by the formula (1) c.

  When a base is used, examples of the base used include sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, cesium carbonate, sodium hydride, triethylamine, pyridine, 4- (dimethylamino) pyridine, and the like. (1) It can be used in the range of 0.1 to 50 equivalents relative to 1 equivalent of the compound represented by c.

  In the case of using a solvent, examples of the solvent used include N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolinone, water and other polar solvents, methanol, Alcohols such as ethanol, propanol, 2-propanol and ethylene glycol, ethers such as diethyl ether, tetrahydrofuran and diphenyl ether, aromatic hydrocarbons such as benzene, toluene and xylene, halogens such as methylene chloride, chloroform and carbon tetrachloride And aliphatic hydrocarbons such as pentahydrocarbons, 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) are known compounds, and some of them are commercially available.

  Manufacturing method E

Among the compounds of the present invention, a compound represented by formula (3) wherein R ⁴ is a hydrogen atom, and formula (9) [wherein R ⁴ represents the same meaning as described above, and Xa represents a leaving group such as a halogen atom. Represents. The compound of the present invention represented by the formula (1) can be produced by reacting the compound represented by the formula (1) with a solvent if necessary and with a base if necessary.

  In this reaction, the compound represented by the formula (9) can be used in the range of 0.5 to 50 equivalents with respect to 1 equivalent of the compound represented by the formula (3).

  When a base is used, examples of the base used include bases such as potassium carbonate, sodium hydride, lithium bis (trimethylsilyl) amide, n-butyllithium, triethylamine, pyridine, 4- (dimethylamino) pyridine, It can be used in the range of 0.1 to 50 equivalents relative to 1 equivalent of the compound represented by (3).

  In the case of using a solvent, examples of the solvent used include N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolinone, water and other polar solvents, methanol, Alcohols such as ethanol, propanol, 2-propanol and ethylene glycol, ethers such as diethyl ether, tetrahydrofuran and diphenyl ether, aromatic hydrocarbons such as benzene, toluene and xylene, halogens such as methylene chloride, chloroform and carbon tetrachloride And aliphatic hydrocarbons such as pentahydrocarbons, 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 (9) are known compounds, and some of them are commercially available.

  Manufacturing method F

Equation (4) [wherein, Q and ^{R 1} are as defined above. And a compound represented by formula (5) a [wherein R ² and R ³ represent the same meaning as described above. The compound represented by formula (3) is reacted by using a solvent if necessary, using a base if necessary and using a condensing agent, wherein Q, R ¹ , R ² and R ³ represents the same meaning as described above. This invention compound represented by this can be manufactured.

  In this reaction, the compound represented by formula (5) a can be used in the range of 0.5 to 100 equivalents with respect to 1 equivalent of the compound represented by formula (4).

  Examples of the condensing agent used include 1H-benzotriazol-1-yloxytris (dimethylamino) phosphonium hexafluorophosphate, N, N′-dicyclohexylcarbodiimide, 1- (3-dimethylaminopropyl) -3- Examples thereof include ethyl carbodiimide hydrochloride, 2-chloro-1-methylpyridinium iodide and the like, and can be used in the range of 0.5 to 50 equivalents with respect to 1 equivalent of the compound represented by formula (5) a.

  When a base is used, as the base to be used, an organic base such as triethylamine, pyridine, 4- (dimethylamino) pyridine, or an inorganic base such as potassium carbonate or sodium carbonate can be used if necessary. Can be used in the range of 0.1 to 50 equivalents relative to 1 equivalent of the compound represented by formula (1).

  When using a solvent, examples of the solvent used include N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolinone, water and other polar solvents, methanol , Alcohols such as ethanol, propanol, 2-propanol, ethylene glycol, ethers such as diethyl ether, tetrahydrofuran, diphenyl ether, aromatic hydrocarbons such as benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, 1 Halogenated hydrocarbons such as 1,2-dichloroethane, 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 (4) are known compounds, and others can be synthesized according to known methods described in the literature. For example, it can be prepared according to the method described in (Journal of Organic Chemistry 2010, 75, 2206, International Publication No. 2009/099929).

  Some of the compounds represented by formula (5) a are known compounds, and some of them are commercially available. Others can also be synthesized according to known methods described in the literature (for example, International Publication No. 2004/048314, International Publication No. 2012/137089).

  Manufacturing method G

Compound represented by formula (4) and formula (6) a wherein R ² and R ³ have the same meaning as described above, and Xa represents a leaving group such as a halogen atom. The compound of the present invention represented by the formula (3) can be produced by reacting the compound represented by the formula (3) with a solvent if necessary and a base if necessary.

  In this reaction, the compound represented by formula (6) a can be used in the range of 0.5 to 100 equivalents with respect to 1 equivalent of the compound represented by formula (4).

  When a base is used, examples of the base used include organic bases such as triethylamine, pyridine, 4- (dimethylamino) pyridine, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, potassium hydroxide, sodium hydroxide. Inorganic bases such as sodium hydride and the like, and can be used in the range of 0.1 to 50 equivalents relative to 1 equivalent of the compound represented by the formula (4).

  When using a solvent, examples of the solvent used include N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolinone, water and other polar solvents, methanol , Alcohols such as ethanol, propanol, 2-propanol, ethylene glycol, ethers such as diethyl ether, tetrahydrofuran, diphenyl ether, aromatic hydrocarbons such as benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, 1 Halogenated hydrocarbons such as 1,2-dichloroethane, 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 (6) a are known compounds, and some of them are commercially available. Others were prepared according to the method described in the literature (for example, Journal of Organic Chemistry 1992, 57, 3463) from the compound represented by formula (5) a shown in the above Production Method F. can do.

  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 chestnut bee 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 taper Common tapeworm (Moniezia benedeni), expanded tapeworm Sheep tapeworm (Moniezia expansa), Stilsia 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, which can be controlled using the compounds of the present invention. 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 aromatic hydrocarbons such as xylene, alkyl (C9 or C10) benzene, phenylxylylethane and alkyl (C1 or C3) naphthalene, fats such as machine oil, normal paraffin, isoparaffin, and naphthene. Aromatic hydrocarbons, 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, polyethylene glycol and Polyhydric alcohol such as polypropylene glycol, propyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol monomethyl ether, propylene glycol Ethers such as rumonoethyl 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, adipic acid Esters such as dialkyl esters and dialkyl phthalates, acid amides such as N-alkyl (C1, C8 or C12) pyrrolidone, oils such as soybean oil, linseed oil, rapeseed oil, coconut oil, cottonseed oil and castor oil, dimethyl sulfoxide As well as 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.

[Milk]
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. 1-01 of the present invention 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. 1-01 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. 1-01 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. 1-01 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] Granules Invention compound No. 1-01 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.

[Composition Example 6] Powder Compound of the present invention No. 1-01 3 parts Carplex # 80D 0.5 part (Synthetic hydrous silicic acid: Shionogi & 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. 1-01 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. 1-01 of the present invention 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. 1-01 2 parts dimethyl sulfoxide 10 parts 2-propanol 35 parts acetone 53 parts [Formulation Example 10] transdermal Solution for administration of the present compound No. 1-01 5 parts hex Lenglycol 50 parts Isopropanol 45 parts [Formulation Example 11] Solution for transdermal administration Compound No. 1-01 of the present invention 5 parts Propylene glycol monomethyl ether 50 parts Dipropylene glycol 45 parts [Formulation example 12] For transdermal administration (drip) Liquid Compound of the Invention Compound No. 1-01 2 parts Light Liquid Paraffin 98 parts [Formulation Example 13] Solution for Transdermal Administration (Drip) Compound No. 1-01 2 parts of 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, fungicides, as necessary, when formulated or sprayed , Plant growth regulators, synergists, fertilizers, soil conditioners, etc. may be mixed and applied.

  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), potassium hydrogen carbonate (potassium hydrogen carbonate), proquinazid (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, pyridaben, pyrimidifen, S-1870 (test name), spirodiclofen, spiromesifen ( spyromesifen), NNI-0711 (test name), CL900187 (test name) and tebufenpyrad.

  Insecticides: abamectin, acephate, acetamipirid, alanamicarb, aldicarb, allethrin, azamethiphos, azinphos-methyl, bacillus tubulin Bacillus thuringiensis, bendiocarb, benfluthrin, benfuracarb, bensultap, bifenthrin, bioallethrin, bioresmethrin, bistrifluron, tris Buprofezin, butocarboxim, carbaryl, carbofuran, carbosulfan, cartap, chlorantraniliprole, Chlorethxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, chromafenozide Clothianidin, cyantraniliprole, cycloprothrin, cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin cyhalothrin), cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, cyromazine, Deltamethrin, diacloden, diafenthiuron, diazinon, dichlorvos, diflubenzuron, dimethylvinphos, dinotefuran, diofenolan, diofenolan Disulfoton, dimethoate, emamectin-benzoate, empenthrin, endosulfan, alpha-endosulfan, EP-N, EPN, esfenvalerate, etiophencarb (Ethiofencarb), ethiprole, etofenprox, etrimfos, fenitrothion, fenobucarb, fenobucarb Fenoxycarb, fenpropathrin, fenthion, fenvalerate, fipronil, flonicamid, flubendiamide, flucythrinate, flufenerim , Flufenoxuron, flufenprox, flumethrin, fluvalinate, tau-fluvalinate, fonophos, formetanate, formotaion ( 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 Protrifenbute, pyrometrozine, pyraclofos, pyrethrins, pyridalalyl, pyrifluquinazon, pyriprole, pyrafluprole, proxy, pyrifiprofen, py Resmethrin, rotenone, SI-0405 (study name), sulprofos, silafluofen, spinetram, spinosad, spirotetramat, sulfoxaflor ), Sulfotep, SYJ-159 (test name), tebfenozide, teflubenzuron, tefluthorin, terbufos, tetrachlorvinphos, tetrame Trimethrin, dT-80-phthalthrin, d-tetramethrin, tetramethylfluthrin, thiacloprid, thiocyclam, thiodicarb, thiamethoxam, thiophanox ( thiofanox, thiometon, tolfenpyrad, tralomethrin, trichlorfon, triazuron, triflumuron, vamidomion and ME-5343 (test name).

  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.

Moreover, the proton nuclear magnetic resonance chemical shift value of the Example was measured at 300 MHz using Me ₄ Si (tetramethylsilane) as a reference material. Moreover, the solvent used for the measurement is described in the following synthesis examples.
[Synthesis example]
Synthesis Example 1: Synthesis of ethyl 3-{[(6-chloro-3-pyridyl) methyl] [2- (3-methylpyridyl)] amino} -2- (4-methoxyphenyl) -3-oxopropionate ( Compound No. 3-22 of the present invention
To a solution of 500 mg of 2- (4-methoxyphenyl) malonic acid monoethyl ester in 5 ml of dichloromethane, 815 mg of oxalyl chloride and a catalytic amount of N, N-dimethylformamide were added and stirred at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure. Dichloromethane was added to the obtained residue and added to a solution of N- (6-chloro-3-pyridylmethyl) -N- (3-methyl-2-pyridyl) amine 333 mg and triethylamine 287 mg in 10 ml of dichloromethane at room temperature. Stir for 2 hours. After completion of the reaction, water was added to the reaction mixture and extracted twice with chloroform. 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 [gradient of 9: 1 to 1: 3 (volume ratio, the same shall apply hereinafter)]. 690 mg of product was obtained as a pale yellow oil.
1H NMR (CDCl ₃ ) δ 8.36 (brs, 1H), 8.14 (brs, 1H), 7.90-7.40 (br, 2H), 7.39-7.15 (m, 2H), 7.02-6.65 (br, 4H), 5.40-4.10 (br, 5H), 3.78 (s, 3H), 2.35-1.45 (br, 3H), 1. 35-1.10 (m, 3H)
Synthesis Example 2: Synthesis of methyl 3-{[(6-chloro-3-pyridyl) methyl] (2-pyridyl) amino) -2- (4-methoxyphenyl) -3-oxopropionate (present compound No. 1) 3-08)
3-{[(6-Chloro-3-pyridyl) methyl] (2-pyridyl) amino} -2- (4-methoxyphenyl) -3-oxopropionate 150 mg of methanol in 1 ml of methanol in 28% by weight sodium 132 mg of methanol solution of methoxide was added and stirred at room temperature for 10 minutes. After completion of the reaction, the solvent was distilled off under reduced pressure. To the obtained residue, 10 ml of a 1N hydrochloric acid aqueous solution was added, and extracted with 10 ml of chloroform. 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 residue was purified by medium pressure preparative liquid silica gel chromatography eluting with n-hexane-ethyl acetate (1: 1) to obtain 39 mg of the desired product as a pale yellow oil.
1H NMR (CDCl ₃ ) δ 8.51 (d, J = 4.7 Hz, 1H), 8.17 (d, J = 2.5 Hz, 1H), 7.70-7.60 (m, 2H), 7 .23 (d, J = 8.3 Hz, 2H), 7.03 (d, J = 8.5 Hz, 2H), 6.95-6.80 (br, 1H), 6.79 (d, J = 8.8 Hz, 2H), 5.06 (d, J = 15.1 Hz, 1H), 4.91 (d, J = 15.1 Hz, 1H), 4.82 (s, 1H), 3.78 ( s, 3H), 3.70 (s, 3H)
Synthesis Example 3: Synthesis of ethyl 3-{[(6-chloro-3-pyridyl) methyl] (2-pyridyl) amino} -2- (2-fluorobenzyl) -3-oxopropionate (present compound No. 1). 2-13)
To a solution of 0.30 g of ethyl 3-{[(6-chloro-3-pyridyl) methyl] (2-pyridyl) amino} -3-oxopropionate in 8.0 g of N, N-dimethylformamide, 0. 27 g and 2-fluorobenzyl bromide 0.19 g were added and stirred at room temperature for 3 days. After completion of the reaction, 10 ml of water and 15 ml of saturated aqueous ammonium chloride solution were added to the reaction mixture, and the mixture was extracted 3 times with 20 ml of diethyl ether. The obtained organic layer was washed twice with 20 ml of water and then dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid silica gel chromatography eluting with n-hexane-ethyl acetate (gradient of 85:15 to 25:75) to give 0.28 g of the objective product as a colorless transparent oil. Obtained as a thing.
1H NMR (CDCl ₃ ) δ 8.44 (dd, J = 4.9, 1.8 Hz, 1H), 8.16 (d, J = 2.4 Hz, 1H), 7.65 (td, J = 8. 2, 2.1 Hz, 1H), 7.55 (dd, J = 8.0, 2.1 Hz, 1H), 7.30-6.70 (m, 7H), 4.98 (d, J = 15 .2 Hz, 1 H), 4.91 (d, J = 15.2 Hz, 1 H), 4.11 (q, J = 7.1 Hz, 2 H), 3.91 (dd, J = 8.5, 7.. 1 Hz, 1H), 3.33-3.15 (m, 2H), 1.19 (t, J = 7.1 Hz, 3H)
Synthesis Example 4: 3-{[(6-chloro-3-pyridyl) methyl] (2-pyridyl) amino} -2-benzyl-3-oxopropionic acid (present compound No. 2-15) and 3- { Synthesis of ethyl [(6-chloro-3-pyridyl) methyl] (2-pyridyl) amino} -2-benzyl-3-oxopropionate (present compound No. 2-14) 60 wt% sodium hydride (mineral oil) Disperse in a solution of 86 mg of tetrahydrofuran in 2 ml of ethyl 3-{[(6-chloro-3-pyridyl) methyl] (2-pyridyl) amino} -3-oxopropionate prepared in a separate container. The solution was added under ice cooling. After completion of the addition, 169 mg of benzyl bromide was added to the reaction mixture under ice cooling. After completion of the addition, the reaction mixture was warmed to room temperature and stirred at room temperature for 2 hours. After completion of stirring, 20 mg of potassium iodide was added to the reaction mixture, and stirring was continued at room temperature for 2 hours. After completion of the reaction, the reaction mixture was extracted with 10 ml of water and 10 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 silica gel chromatography eluting with n-hexane-ethyl acetate (gradient 6: 4 to 4: 6) to obtain the desired product 3-{[(6-chloro 161 mg of ethyl-3-pyridyl) methyl] (2-pyridyl) amino} -2-benzyl-3-oxopropionate was obtained as a colorless transparent liquid.

Further, an aqueous 1M hydrochloric acid solution was added to the aqueous layer obtained by extraction after the completion of the reaction under ice cooling, and the aqueous layer whose pH was adjusted to about 4 was extracted with 20 ml of ethyl acetate. The obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the desired product 3-{[(6-chloro-3-pyridyl) methyl] (2-pyridyl) amino} was obtained. 59 mg of 2-benzyl-3-oxopropionic acid was obtained as a white solid. Melting point 135-137 ° C
The 1 H NMR of ethyl 3-{[(6-chloro-3-pyridyl) methyl] (2-pyridyl) amino} -2-benzyl-3-oxopropionate is shown below.
1H NMR (CDCl ₃ ) δ 8.45 (d, J = 3.1 Hz, 1H), 8.15 (d, J = 2.4 Hz, 1H), 7.60 (dt, J = 7.7, 1. 9 Hz, 1H), 7.52 (d, J = 6.8 Hz, 1H), 7.25-7.15 (m, 5H), 7.10-7.00 (m, 2H), 6.60 ( brs, 1H), 4.95 (s, 2H), 4.12 (q, J = 7.2 Hz, 2H), 3.76 (dd, J = 9.0, 6.0 Hz, 1H), 3. 35-3.10 (m, 2H), 1.20 (t, J = 7.2 Hz, 3H)
Synthesis Example 5 Synthesis of ethyl 3-{[(6-chloro-3-pyridyl) methyl] (2-pyridyl) amino} -2- (2-nitro-4-trifluoromethylphenyl) -3-oxopropionate (Invention compound No. 3-33)
3-{[((6-Chloro-3-pyridyl) methyl] (2-pyridyl) amino} -3-oxo prepared in a separate container in a solution of 60% by weight sodium hydride (dispersed in mineral oil) 46 mg in tetrahydrofuran 2 ml A solution of 177 mg of ethyl propionate in 1 ml of tetrahydrofuran was added under ice cooling. After completion of the addition, the reaction mixture was warmed to room temperature, 131 mg of 1-chloro-2-nitro-4- (trifluoromethyl) benzene was added to the reaction mixture at room temperature, and stirring was continued for 10 minutes. After completion of the stirring, the reaction mixture was continuously stirred at 60 degrees for 5 hours. After completion of the stirring, the reaction mixture was stirred overnight at room temperature. After completion of the stirring, the reaction mixture was continuously stirred at 60 degrees for 3 hours. After completion of the reaction, the reaction mixture was extracted with 10 ml of 1M aqueous hydrochloric acid and 10 ml of ethyl acetate. The obtained organic layer was 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 silica gel chromatography eluting with n-hexane-ethyl acetate (gradient 6: 4 to 4: 6) to obtain the desired product 3-{[(6-chloro 59 mg of ethyl-3-pyridyl) methyl] (2-pyridyl) amino} -2- (2-nitro-4-trifluoromethylphenyl) -3-oxopropionate was obtained as a colorless transparent liquid.
1H NMR (CDCl ₃ ) δ 8.40-8.35 (m, 1H), 8.25 (d, J = 2.5 Hz, 1H), 8.19 (s, 1H), 7.89 (s, 2H) ), 7.80-7.65 (m, 2H), 7.30-7.20 (m, 2H), 7.09 (d, J = 7.7 Hz, 1H), 5.56 (s, 1H) ), 5.20 (d, J = 15.3 Hz, 1H), 4.91 (d, J = 15.4 Hz, 1H), 4.25 (qd, J = 7.2, 2.2 Hz, 2H) , 1.26 (t, J = 7.2 Hz, 3H)
Synthesis Example 6 Synthesis of ethyl 3-{[(6-chloro-3-pyridyl) methyl] (2-pyridyl) amino} -2- (4-methoxyphenyl) -2-methyl-3-oxopropionate Invention compound No. 2-10)
3-{[(6-Chloro-3-pyridyl) methyl] (2-pyridyl) amino} -2- (2) prepared in a separate container in a solution of 27 mg of 60 wt% sodium hydride (dispersed in mineral oil) in 10 ml of tetrahydrofuran 200 ml of ethyl 4-methoxyphenyl) -3-oxopropionate in 3 ml of tetrahydrofuran was added under ice cooling. After the addition was complete, the reaction mixture was warmed to room temperature and stirred for 15 minutes. After completion of stirring, 196 mg of methyl iodide was added to the reaction mixture, and stirring was continued at room temperature for 16 hours. After completion of the reaction, the reaction mixture was poured into ice water and extracted with 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 silica gel chromatography eluting with n-hexane-ethyl acetate (gradient 9: 1 to 1: 3) to obtain 100 mg of the desired product as a pale yellow oil. It was.
_{1H NMR (CDCl 3) δ8.42-8.08 (} m, 2H), 7.72-7.57 (m, 1H), 7.45-7.18 (m, 4H), 7.05-6 .95 (m, 1H), 6.70-6.35 (m, 3H), 5.22 (d, J = 15.3 Hz, 1H), 4.68 (d, J = 15.6 Hz, 1H) 4.27-4.12 (m, 2H), 3.76 (s, 3H), 1.80 (s, 3H), 1.28 (t, J = 7.2 Hz, 3H)
Synthesis Example 7 Synthesis of N1-[(6-chloro-3-pyridyl) methyl] -N3-methyl-2- (4-methoxyphenyl) -N1- (2-pyridyl) malonamide (present compound No. 3- 11)
To a solution of 268 mg of 2- (4-methoxyphenyl) -3- (methylamino) -3-oxopropanoic acid in 5 ml of 1,2-dichloroethane, 289 mg of triethylamine, benzotriazol-1-yloxytris (dimethylamino) phosphonium hexa 631 mg of fluorophosphate and 150 mg of 6-chloro-N-2-pyridinyl-3-pyridinemethanamine were sequentially added and stirred overnight at room temperature. After completion of the reaction, the reaction mixture was poured into 10 ml of water and extracted with 10 ml of chloroform. The obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The resulting residue was purified by medium pressure preparative liquid silica gel chromatography eluting with n-hexane-ethyl acetate (1: 0 to 0: 1 gradient) and then ethyl acetate-methanol (4: 1), The target product (274 mg) was obtained as a pale yellow oil.
1H NMR (CDCl ₃ ) δ 8.51 (d, J = 3.1 Hz, 1H), 8.18 (d, J = 2.7 Hz, 1H), 7.70-7.60 (m, 2H), 7 .30-7.20 (m, 3H), 7.12 (d, J = 8.9 Hz, 2H), 6.95-6.80 (br, 1H), 6.81 (d, J = 8. 9 Hz, 2H), 5.02 (s, 2H), 4.52 (s, 1H), 3.78 (s, 3H), 2.78 (d, J = 4.8 Hz, 3H)
Synthesis Example 8 Synthesis of ethyl 3-{[(6-fluoro-3-pyridyl) methyl] (2-pyridyl) amino} -2- (2-methoxy-5-trifluoromethylphenyl) -3-oxopropionate (Invention compound No. 3-03)
To a solution of 500 mg of 2- (2-methoxy-5-trifluoromethylphenyl) malonic acid monoethyl ester and 365 mg of 6-fluoro-N-2-pyridinyl-3-pyridinemethanamine in 5 ml of 1,2-dichloroethane, benzotriazole -1-yloxytris (dimethylamino) phosphonium hexafluorophosphate (955 mg) and triethylamine (1.1 g) were sequentially added, and the mixture was stirred overnight at room temperature. After completion of the reaction, 10 ml of water was added to the reaction mixture and extracted with 10 ml of chloroform. 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 silica gel column eluting with n-hexane-ethyl acetate (1: 0 to 0: 1 gradient) to obtain 39 mg of the objective product as a colorless transparent liquid. It was.
1H NMR (CDCl ₃ ) δ 8.48 (d, J = 3.4 Hz, 1H), 8.01 (s, 1H), 7.86 (brs, 1H), 7.70-7.60 (m, 2H) ), 7.50 (dd, J = 8.7, 1.7 Hz, 1H), 7.30-7.15 (m, 1H), 6.90-6.75 (m, 3H), 5.31. (S, 1H), 5.09 (d, J = 15.1 Hz, 1H), 4.98 (d, J = 15.1 Hz, 1H), 4.22 (q, J = 7.0 Hz, 2H) 3.63 (s, 3H), 1.25 (t, J = 7.0 Hz, 3H)
Synthesis Example 9 Synthesis of ethyl 3-{[(6-chloro-3-pyridyl) methyl] (2-pyridyl) amino} -2- (4-hydroxyphenyl) -3-oxopropionate (present compound No. 1) 3-06)
To a solution of 3.00 g of ethyl 3-{[(6-chloro-3-pyridyl) methyl] (2-pyridyl) amino} -3- (4-methoxyphenyl) -3-oxopropionate in 50 ml of dichloromethane under ice-cooling. 13.6 ml of about 1M boron tribromide in dichloromethane was added. After completion of the addition, the mixture was stirred at room temperature for 16 hours. After completion of the reaction, water was added to the reaction mixture and extracted with chloroform. 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 silica gel chromatography eluting with n-hexane-ethyl acetate (gradient 9: 1 to 1: 3) to give 1.50 g of the desired product as a pale yellow oil. Got as.
1H NMR (CDCl ₃ ) δ 8.50 (dd, J = 4.8, 1.5 Hz, 1H), 8.18 (d, J = 2.4 Hz, 1H), 7.70-7.64 (m, 2H), 7.30-7.20 (m, 2H), 7.00-6.80 (m, 3H), 6.61 (d, J = 6.6 Hz, 2H), 6.53 (s, 1H), 5.10 (d, J = 15.0 Hz, 1H), 4.89 (d, J = 15.0 Hz, 1H), 4.77 (s, 1H), 4.22-4.08 ( m, 2H), 1.22 (t, J = 7.2 Hz, 3H)
Synthesis Example 10: 3-{[(6-Chloro-3-pyridyl) methyl] (2-pyridyl) amino} -2- (4-ethoxyphenyl) -3-oxopropionate (present compound No. 3- 13) and 3-{[(6-chloro-3-pyridyl) methyl] (2-pyridyl) amino} -2- (4-ethoxyphenyl) -2-ethyl-3-oxopropionate (the present compound No. Synthesis of 2-11) 3-{[(6-Chloro-3-pyridyl) methyl] (2-pyridyl) amino} -2- (4-hydroxyphenyl) -3-oxopropionate 200 mg of acetonitrile in 10 ml solution Were added 220 mg of iodoethane and 459 mg of cesium carbonate. After completion of the addition, the mixture was stirred for 1 hour under heating and reflux. After completion of the reaction, water was added to the reaction mixture and extracted twice with chloroform. 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 resulting residue was purified by medium pressure preparative liquid silica gel chromatography eluting with n-hexane-ethyl acetate (9: 1 to 1: 3 gradient) to give 3-{[(6-chloro-3 -Pyridyl) methyl] (2-pyridyl) amino} -2- (4-ethoxyphenyl) -3-oxopropionate 70 mg and 3-{[(6-chloro-3-pyridyl) methyl] (2-pyridyl) Amino} -2- (4-ethoxyphenyl) -2-methyl-3-oxopropionate (25 mg) was obtained as a pale yellow oil.

3-{[(6-Chloro-3-pyridyl) methyl] (2-pyridyl) amino} -2- (4-ethoxyphenyl) -3-oxopropionate 1H NMR (CDCl ₃ ) δ 8.50 (dd, J = 4.8, 1.2 Hz, 1H), 8.18 (d, J = 2.4 Hz, 1H), 7.64 (ddd, J = 7.5, 7.5, 2.1 Hz, 2H) 7.26-7.18 (m, 2H), 7.02 (d, J = 8.7 Hz, 2H), 6.88 (brs, 1H), 6.75 (d, J = 8.7 Hz, 2H), 5.10 (d, J = 15.3 Hz, 1H), 4.88 (d, J = 15.3 Hz, 1H), 4.79 (s, 1H), 4.20-4.08 ( m, 2H), 3.99 (q, J = 7.2 Hz, 2H), 1.38 (t, J = 7.2 Hz, 3H), 1.21 (t, J = 7.2 Hz, H)
3-{[(6-Chloro-3-pyridyl) methyl] (2-pyridyl) amino} -2- (4-ethoxyphenyl) -2-ethyl-3-oxopropionate 1H NMR (CDCl ₃ ) δ8. 31-8.00 (m, 2H), 7.60-7.10 (m, 5H), 7.02-6.92 (m, 1H), 6.61 (d, J = 8.7 Hz, 2H) ), 6.36 (brs, 1H), 5.20 (d, J = 15.6 Hz, 1H), 4.64 (d, J = 15.3 Hz, 1H), 4.33-4.07 (m , 2H), 4.02-3.83 (m, 2H), 2.53-2.28 (m, 1H), 2.26-2.02 (m, 1H), 1.38 (t, J = 6.9 Hz, 3H), 1.30 (t, J = 7.2 Hz, 3H), 0.64 (t, J = 7.5 Hz, 3H)
Synthesis Example 11 Synthesis of ethyl 3-{[(6-chloro-3-pyridyl) methyl] (2-pyridyl) amino} -2- (4-chlorophenyl) -3-oxopropionate (Compound No. 3 of the present invention) -05)
A solution of 350 mg of 2- (4-chlorophenyl) -N-[(6-chloro-3-pyridyl) methyl] -N- (2-pyridyl) acetamide in 10 ml of tetrahydrofuran was cooled to −78 ° C., and 1.1 M lithium bis 1.28 ml of a tetrahydrofuran solution of (trimethylsilyl) amide was added. After the addition was complete, the reaction mixture was stirred at the same temperature for 45 minutes. After completion of the stirring, 204 mg of ethyl chloroformate was added to the reaction mixture at the same temperature. After completion of the addition, the reaction mixture was warmed to room temperature and stirred for 16 hours. After completion of the reaction, the reaction mixture was poured into ice water and extracted with chloroform. 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 silica gel column eluting with n-hexane-ethyl acetate (gradient 9: 1 to 1: 3) to obtain 200 mg of the desired product as a yellow oil. .
1H NMR (CDCl ₃ ) δ 8.50 (dd, J = 5.1, 2.1 Hz, 1H), 8.18 (d, J = 2.4 Hz, 1H), 7.75-7.63 (m, 2H), 7.32-7.18 (m, 4H), 7.08 (d, J = 8.7 Hz, 2H), 7.02-6.86 (br, 1H), 5.13 (d, J = 15.0 Hz, 1H), 4.85 (d, J = 15.0 Hz, 1H), 4.85 (s, 1H), 4.25-4.05 (m, 2H), 1.21 ( t, J = 7.2 Hz, 3H)
Synthesis Example 12 Synthesis of 2- (4-methoxyphenyl) -2-methylsulfonyl-N-[(6-chloro-3-pyridyl) methyl] -N- (2-pyridyl) acetamide (Compound No. 3 of the present invention) -29)
A solution of 500 mg of 2- (4-methoxyphenyl) -N-[(6-chloro-3-pyridyl) methyl] -N- (2-pyridyl) acetamide in 10 ml of tetrahydrofuran was cooled to −78 ° C., and 1.1 M lithium was added. 3.00 ml of a tetrahydrofuran solution of bis (trimethylsilyl) amide was added. After completion of the addition, the reaction mixture was stirred at the same temperature for 30 minutes. After completion of stirring, 467 mg of methanesulfonyl chloride was added to the reaction mixture at the same temperature. After completion of the addition, the reaction mixture was warmed to room temperature and stirred at room temperature for 16 hours. After completion of the reaction, the reaction mixture was poured into ice water and extracted with chloroform. 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 silica gel chromatography eluting with n-hexane-ethyl acetate (gradient 9: 1 to 1: 3) to obtain 360 mg of the desired product as a yellow oil. .
1H NMR (CDCl ₃ ) δ 8.49-8.44 (m, 1H), 8.22 (d, J = 2.4 Hz, 1H), 7.77-7.65 (m, 2H), 7.38 -7.23 (m, 4H), 6.98-6.85 (m, 3H), 5.17 (d, J = 15.3 Hz, 1H), 5.01 (d, J = 15.3 Hz, 1H), 4.99 (s, 1H), 3.82 (s, 3H), 2.98 (s, 3H)
Synthesis Example 13 Synthesis of 2- (4-chlorophenyl) -N-[(6-chloro-3-pyridyl) methyl] -N- (2-pyridyl) acetamide (present compound No. 9-02)
N-[(6-Chloro-3-pyridyl) methyl] -N- (2-pyridyl) prepared in a separate container in a solution of 273 mg of N, N-dimethylformamide in 273 mg sodium hydride (dispersed in mineral oil) ) 3 ml of N, N-dimethylformamide 1.00 g of amine was added under ice cooling. After completion of the addition, the reaction mixture was warmed to room temperature and stirred at room temperature for 10 minutes. To the reaction mixture, 1.29 g of 4-chlorophenylacetyl chloride was added, and stirring was further continued at room temperature for 14 hours. After completion of the reaction, the reaction mixture was poured into ice water and extracted with diethyl ether. The obtained organic layer was washed and dried in the order of 1N aqueous hydrochloric acid solution, saturated brine and then anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by medium pressure preparative liquid silica gel chromatography eluting with n-hexane-ethyl acetate (9: 1 to 1: 3 gradient) to obtain 560 mg of the desired product as a pale yellow oil.
1H NMR (CDCl ₃ ) δ 8.52 (dd, J = 4.8, 1.5 Hz, 1H), 8.16 (d, J = 2.4 Hz, 1H), 7.80-7.59 (m, 2H), 7.30-7.16 (m, 4H), 6.99 (d, J = 8.4 Hz, 2H), 6.94 (brs, 1H), 5.00 (s, 2H), 3 .59 (s, 2H)
Synthesis Example 14 Synthesis of N- (2-pyridyl) -N-((5-pyrimidinyl) methyl) -2- (3- (trifluoromethyl) phenyl) acetamide (Compound No. 11-01 of the present invention)
2.60 g of oxalyl chloride and a catalytic amount of N, N-dimethylformamide were added to a solution of 1.10 g of 2- (3- (trifluoromethyl) phenyl) acetoacetic acid in 30 ml of dichloromethane, and the mixture was added with ice cooling for 30 minutes. Stir. After completion of the reaction, the solvent was distilled off under reduced pressure. To the obtained residue was added 5 ml of dichloromethane, and N- (2-pyridyl) -N-((5-pyrimidinyl) methyl) amine was added to a solution of 840 mg of dichloromethane and 14 ml of 1M aqueous sodium hydroxide solution. Stir for hours. After completion of the reaction, water was added to the reaction mixture and extracted twice with chloroform. The obtained organic layer was washed and dried in the order of 1N aqueous hydrochloric acid solution, 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 9: 1 to 1: 3) to obtain 764 mg of the desired product as a pale yellow oil. .
1H NMR (CDCl ₃ ) δ 9.09 (s, 1H), 8.67 (s, 2H), 8.55 (dd, J = 4.9, 1.0 Hz, 1H), 7.74 (ddd, J = 7.8, 7.7, 1.7 Hz, 1H), 7.57-7.40 (m, 2H), 7.40-7.27 (m, 2H), 7.20 (s, 1H) 7.01 (d, J = 7.8 Hz, 1H), 5.02 (s, 2H), 3.71 (s, 2H)
This invention compound can be manufactured according to the said manufacturing method and an Example. Although the example of this invention compound manufactured similarly to the synthesis examples 1-14 is shown in Table 1 thru | or Table 11, this invention is not limited only to these. In the table, “Me” represents a methyl group, and similarly, Et represents an ethyl group, n-Pr represents a normal propyl group, i-Pr represents an isopropyl group, i-Bu represents an isobutyl group, sec − Bu is secondary butyl group, t-Bu is tertiary butyl group, Bn is benzyl group, Tf is trifluoromethylsulfonyl group, Nf is nonafluoronormal butylsulfonyl group, Ac is acetyl group, Ph is Each represents a phenyl group. In addition,-in the table indicates that there is no substitution. The substituents represented by D-1 to D-10 in the table each represent the following structure.

[Table 1]

――――――――――――――――――――――――――
No. R ¹
――――――――――――――――――――――――――
1-01 D-1
1-02 D-9
1-03 D-10
――――――――――――――――――――――――――
(Table 2)

―――――――――――――――――――――――――――――――――――――
No. R ² R ³ R ⁴
―――――――――――――――――――――――――――――――――――――
2-01 HHC (O) OEt
2-02 Me HC (O) OEt
2-03 i-Pr HC (O) OEt
2-04 t-Bu HC (O) OEt
2-05 D-2 HC (O) OEt
2-06 CH ₂ (Ph-4-OMe) HC (O) OEt
2-07 CH ₂ (Ph-2,6-F ₂ ) HC (O) OEt
2-08 D-3 HC (O) OEt
2-09 D-4 HC (O) OEt
2-10 Ph-4-OMe Me C (O) OEt
2-11 Ph-4-OEt Et C (O) OEt
2-12 CH ₂ (Ph-2-Cl-5-F) HC (O) OEt
2-13 CH ₂ (Ph-2-F) HC (O) OEt
2-14 Bn HC (O) OEt
2-15 Bn HC (O) OH
2-16 CH ₂ (Ph-2-F) HP (O) (OEt) ₂
2-17 C (O) Ph HC (O) OEt
―――――――――――――――――――――――――――――――――――――
(Table 3)

―――――――――――――――――――――――――――――――――――――
No. (W) p ₁ (X) q ₁ (Z) r ₁ R ⁴
―――――――――――――――――――――――――――――――――――――
3-01 − 6-F 4-OMe C (O) OEt
3-02 − 6-F 3,5- (OMe) ₂ C (O) OEt
3-03 − 6-F 2-OMe, 5-CF ₃ C (O) OEt
3-04 − 6-Cl 3-OMe C (O) OEt
3-05-6-Cl 4-Cl C (O) OEt
3-06 − 6-Cl 4-OH C (O) OEt
3-07 − 6-Cl 4-OMe Ac
3-08 − 6-Cl 4-OMe C (O) OMe
3-09 − 6-Cl 4-OMe C (O) OEt
3-10 − 6-Cl 4-OMe C (O) O (n-Pr)
3-11 − 6-Cl 4-OMe C (O) NHMe
3-12 − 6-Cl 4-OMe C (O) NMe ₂
3-13 − 6-Cl 4-OEt C (O) OEt
3-14 − 6-Cl 4-O (i-Pr) C (O) OEt
3-15 − 6-Cl 4-OCH ₂ OMe C (O) OEt
3-16 − 6-Cl 4-OC (O) Me C (O) OEt
3-17 − 6-Cl 4-OTf C (O) OEt
3-18 − 6-Cl 4-ONf C (O) OEt
3-19 − 6-Cl 3,5- (Me) ₂ C (O) OEt
3-20 − 6-Cl 3,5- (OMe) ₂ C (O) OEt
3-21 3-F 6-Cl 4-OMe C (O) OEt
3-22 3-Me 6-Cl 4-OMe C (O) OEt
3-23 3-Me 6-Cl 4-OMe C (O) NMe ₂
3-24 3-Me 6-Cl 4-OMe C (O) D-5
3-25 3-Me 6-Cl 3,5- (Me) ₂ C (O) OEt
3-26 4-Me 6-Cl 4-OMe C (O) OEt
3-27 5-Me 6-Cl 4-OMe C (O) OEt
3-28 6-Me 6-Cl 4-OMe C (O) OEt
3-29 − 6-Cl 4-OMe S (O) ₂ Me
3-30 − 6-Cl 4-CF ₃ C (O) OEt
3-31 − 6-Cl 2,5- (OMe) ₂ C (O) OEt
3-32 − 6-Cl 3,4- (OMe) ₂ C (O) OEt
3-33 − 6-Cl 2-NO ₂ , 4-CF ₃ C (O) OEt
3-34 − 6-Cl 4-OMe C (O) NHCH ₂ CF ₃
3-35 − 6-Cl 3-Et C (O) OEt
3-36 − 6-Cl 3-OCF ₃ C (O) OEt
3-37 − 6-Cl 2-F, 5-CF ₃ C (O) OEt
3-38 − 6-Cl 2-CF ₃ , 5-Cl C (O) OEt
3-39 − 6-Cl 4-Br C (O) OEt
3-40 − 6-Cl 4-NMe ₂ C (O) OEt
3-41 − 6-Cl 2-OMe, 5-OCF ₃ C (O) OEt
3-42 − 6-Cl 3-Br, 4-OMe C (O) OEt
3-43 − 6-Cl 4-OMe C (O) S (n-Pr)
3-44 − 6-Cl 3-Me C (O) S (n-Pr)
3-45 − 6-Cl 4-OMe C (O) NHEt
3-46 − 6-Cl 4-FC (O) OEt
3-47 − 6-Cl 3-FC (O) OEt
3-48 − 6-Cl 2-FC (O) OEt
3-49 − 6-Cl 2,4- (F) ₂ C (O) OEt
3-50 − 6-Cl 4-Me C (O) OEt
3-51 − 6-Cl 3-Me C (O) OEt
3-52 − 6-Cl 2-Me C (O) OEt
3-53 − 6-Cl 3-F, 5-Me C (O) OEt
3-54 − 6-Cl 3- (D-6), 4-OMe C (O) OEt
3-55 − 6-Cl 3-Cl C (O) OEt
3-56 − 6-Cl 2-Cl C (O) OEt
3-57 − 6-Cl 4-OPh C (O) OEt
3-58 − 6-Cl 3-OPh C (O) OEt
3-59 − 6-Cl 2-OPh C (O) OEt
3-60 − 6-Cl 4-SMe C (O) OEt
3-61 − 6-Cl 4-S (O) Me C (O) OEt
3-62 − 6-Cl 4-SO ₂ Me C (O) OEt
―――――――――――――――――――――――――――――――――――――
(Table 4)

―――――――――――――――――――――――――――――――――――――
No. (W) p ₁ (X) q ₂ (Z) r ₁ R ⁴
―――――――――――――――――――――――――――――――――――――
4-01 − 2-Cl 3-OMe C (O) OEt
4-02 − 2-Cl 4-OMe C (O) OEt
4-03 − 2-Cl 3,5- (Me) ₂ C (O) OEt
4-04 − 2-Cl 3,5- (OMe) ₂ C (O) OEt
4-05 3-Me 2-Cl 4-OMe C (O) OEt
4-06 3-Me 2-Cl 3,5- (Me) ₂ C (O) OEt
4-07 3-Me 2-Cl 3,5- (Me) ₂ C (O) OMe
4-08 − 2-Cl 4- t-Bu C (O) OEt
4-09 − 2-Cl 3- Et C (O) OEt
4-10 3-Me 2-Cl 2-Me C (O) OEt
4-11 − 2-Cl 3-OCF ₃ , 5- (D-7) C (O) OEt
4-12 − 2-Cl 3-OCF ₃ , 5- (D-6) C (O) OEt
4-13 − 2-Cl 3- (D-6), 4-FC (O) OEt
4-14 − 2-Cl 3-OCF ₃ , 5- (D-6) C (O) S (n-Pr)
4-15 − 2-Cl 3- (D-8), 4-FC (O) OEt
4-16 − 2-Cl 3- (D-8), 4-FC (O) S (n-Pr)
4-17 − 2-Cl 3-OTf C (O) OEt
4-18 − 2-Cl 2-F, 4-Cl C (O) OEt
4-19 − 2-Cl 3-F, 5-Me C (O) S (n-Pr)
4-20 − 2-Cl 3-OMe C (O) SMe
4-21 − 2-Cl 3-OMe C (O) S (n-Pr)
4-22 − 2-Cl 3-OMe C (O) S (i-Pr)
4-23 − 2-Cl 3-OMe C (O) S (n-Bu)
4-24 − 2-Cl 3-OMe C (O) S (t-Bu)
4-25 − 2-Cl 3-OMe C (O) S (i-Bu)
4-26 − 2-Cl 3-OMe C (O) S (sec-Bu)
4-27 − 2-Cl 3- CF ₃ C (O) OEt
4-28 − 2-Cl 3-CF ₃ C (O) S (n-Pr)
4-29 − 2-Cl 3,5- (CF ₃ ) ₂ C (O) S (n-Pr)
4-30 − 2-Cl 3,5- (OMe) ₂ C (O) S (n-Pr)
4-31 − 2-Cl 3,5- (OMe) ₂ C (O) S (t-Bu)
4-32 − 2-Cl 4-SO ₂ CF ₃ C (O) OEt
4-33 − 2-Cl 2-F, 4-OMe C (O) OEt
4-34 − 2-Cl 4-Cl C (O) OEt
4-35 − 2-Cl 3-OMe C (O) Ph
―――――――――――――――――――――――――――――――――――――
(Table 5)

―――――――――――――――――――――――――――――――――――――
No. (W) p ₂ (X) q ₁ (Z) r ₁ R ⁴
―――――――――――――――――――――――――――――――――――――
5-01 − 6-Cl 4-OMe C (O) OEt
5-02 5-Me 6-Cl 4-OMe C (O) OEt
―――――――――――――――――――――――――――――――――――――
[Table 6]

―――――――――――――――――――――――――――――――――――――
No. (W) p ₂ (X) q ₂ (Z) r ₁ R ⁴
―――――――――――――――――――――――――――――――――――――
6-01 − 2-Cl 3-OMe C (O) S (n-Pr)
―――――――――――――――――――――――――――――――――――――
[Table 7]

―――――――――――――――――――――――――――――――――――――
No. (W) p ₁ (X) q ₂ (Z) r ₁ R ⁴
―――――――――――――――――――――――――――――――――――――
7-01 − 2-Cl − C (O) OEt
7-02 − 2-Cl − C (O) OH
―――――――――――――――――――――――――――――――――――――
[Table 8]

―――――――――――――――――――――――――――――――――――――
No. (W) p ₁ (X) q ₄ (Z) r ₁ R ⁴
―――――――――――――――――――――――――――――――――――――
8-01 − − CF ₃ C (O) S (n-Pr)
―――――――――――――――――――――――――――――――――――――
[Table 9]

―――――――――――――――――――――――――――――――――――――
No. (W) p ₁ (X) q ₁ (Z) r ₁
―――――――――――――――――――――――――――――――――――――
9-01 − 6- Cl 4- CF ₃
9-02 − 6- Cl 4-Cl
9-03 − 6- Cl 4- Br
9-04 − 6- Cl 4- SMe
9-05 − 6- Cl 4- SO ₂ Me
9-06 − 6- Cl 3-Cl
9-07 − 6- Cl 3- OMe
9-08 − 6- Cl 2- F
9-09 − 6- Cl 3,4- (OMe) ₂
9-10 − 6- Cl 2,5- (OMe) ₂
9-11 − 6- Cl 3-Br, 4-OMe
9-12 − 6- Cl 2- OMe, 5-OCF ₃
9-13 − 6- Cl 3- (D-6), 4-OMe
―――――――――――――――――――――――――――――――――――――
[Table 10]

―――――――――――――――――――――――――――――――――――――
No. (W) p ₁ (X) q ₂ (Z) r ₁
―――――――――――――――――――――――――――――――――――――
10-01 − 2-Cl 4-OCF ₃
10-02 − 2-Cl 4- t-Bu
10-03 − 2-Cl 3- CF ₃
10-04 3-Me 2-Cl 2-Me
10-05 3-Me 2-Cl 3,5- (Me) ₂
10-06 − 2-Cl 3,5- (OMe) ₂
10-07 − 2-Cl 3-F, 5-Me
10-08 - 2-Cl 3-OCF 3, 5- (D-6)
10-09 − 2-Cl 2-F, 4-OMe
10-10 − 2-Cl 2-F, 4-Cl
―――――――――――――――――――――――――――――――――――――
[Table 11]

―――――――――――――――――――――――――――――――――――――
No. (W) p ₁ (X) q ₄ (Z) r ₁
―――――――――――――――――――――――――――――――――――――
11-01 − − 3- CF ₃
―――――――――――――――――――――――――――――――――――――
Tables 12 and 13 show ¹ H-NMR data or logP values of the compounds of the present invention.

The proton nuclear magnetic resonance chemical shift value was measured at 300 MHz in deuterated chloroform solvent using Me ₄ Si (tetramethylsilane) as a reference substance.

logP is measured according to OECD GUIDINES FOR THE TESTING CHEMICALS Partition Coefficient (n-octanol / water), High Performance Liquid Chromatography (HPLC) 13 Measurement was performed by liquid chromatography. As logP known standard substances, thiourea, benzyl alcohol, nitrobenzene, toluene, benzophenone, naphthalene, and biphenyl were used.
The measurement conditions are as follows.
Apparatus: Agilent 1100 Series HPLC
Column: GL Science's Inertsil ODS-3 particle size 5um, inner diameter 4.6mm, length 33mm
Mobile phase: A mixture of acetonitrile and 0.1 M acetic acid-sodium acetate buffer aqueous solution of pH 6 {mixing ratio 1: 1 (volume ratio)}
Oven temperature: 45 ° C
Flow rate: 2 ml / min
[Table 12]
―――――――――――――――――――――――――――――――――――――――
No. Proton nuclear magnetic resonance chemical shift value (CDCl ₃ Middle): σ (ppm)
―――――――――――――――――――――――――――――――――――――――
1-01; δ 8.52 (d, J = 4.8 Hz, 1H), 7.69 (t, J = 7.5 Hz, 1H), 7.30-7.20 (m, 1H), 7.10 −6.90 (m, 3H), 6.76 (d, J = 7.5 Hz, 2H), 4.74 (s, 1H), 4.25 to 3.58 (m, 10H), 3.51 -3.31 (m, 1H), 2.62-2.42 (m, 1H), 2.05-1.82 (m, 1H), 1.73-1.50 (m, 1H), 1 .23 (t, J = 7.5 Hz, 3H)
2-01; δ 8.49 (d, J = 3.8 Hz, 1H), 8.23 (s, 1H), 7.80-7.68 (m, 2H), 7.30-7.20 (m , 2H), 7.12 (d, J = 7.8 Hz, 1H), 5.09 (s, 2H), 4.13 (q, J = 7.2 Hz, 2H), 3.49 (s, 2H) ), 1.23 (t, J = 7.2 Hz, 3H)
2-02; δ 8.52 (d, J = 2.1 Hz, 1H), 8.22 (d, J = 2.4 Hz, 1H), 7.78-7.69 (m, 2H), 7.30 −7.20 (m, 2H), 7.11 (d, J = 7.8 Hz, 1H), 5.23 (d, J = 15.0 Hz, 1H), 4.87 (d, J = 15. 0 Hz, 1H), 4.10 (q, J = 7.2 Hz, 2H), 3.57 (q, J = 7.2 Hz, 1H), 1.40 (d, J = 7.2 Hz, 3H), 1.20 (t, J = 7.2 Hz, 3H)
2-03; δ 8.53 (d, J = 2.1 Hz, 1H), 8.23 (d, J = 2.4 Hz, 1H), 7.78-7.69 (m, 2H), 7.30 −7.20 (m, 2H), 7.20−7.03 (br, 1H), 5.15 (d, J = 15.0 Hz, 1H), 4.93 (d, J = 15.0 Hz, 1H), 4.13 (q, J = 7.2 Hz, 2H), 3.15 (d, J = 9.3 Hz, 1H), 2.57-2.40 (m, 1H), 1.21 ( t, J = 7.2 Hz, 3H), 1.00-0.80 (m, 6H)
2-04; δ 8.53 (d, J = 2.1 Hz, 1H), 8.21 (d, J = 2.4 Hz, 1H), 7.80-7.68 (m, 2H), 7.30 −7.20 (m, 2H), 7.06 (d, J = 7.8 Hz, 1H), 5.22 (d, J = 15.6 Hz, 1H), 4.84 (d, J = 15. 6 Hz, 1H), 4.16 (q, J = 7.2 Hz, 2H), 3.27 (s, 1H), 1.25 (t, J = 7.2 Hz, 3H), 1.04 (s, 9H)
2-05; δ 8.62-8.47 (m, 1H), 8.23 (d, J = 2.1 Hz, 1H), 7.82-7.63 (m, 2H), 7.36-7 0.00 (m, 3H), 5.80-5.60 (m, 1H), 5.60-5.45 (m, 1H), 5.32-5.10 (m, 1H), 5.10 -4.80 (m, 1H), 4.27-4.06 (m, 2H), 3.42-3.20 (m, 1H) 3.10-2.92 (m, 1H), 2. 10-1.10 (m, 9H)
2-06; δ 8.45 (dd, J = 4.8, 1.5 Hz, 1H), 8.15 (d, J = 2.4 Hz, 1H), 7.61 (td, J = 7.7, 1.5 Hz, 1H), 7.51 (d, J = 6.8 Hz, 1H), 7.25-7.12 (m, 2H), 6.95 (d, J = 8.6 Hz, 2H), 6.75-6.55 (m, 1H), 6.73 (d, J = 8.6 Hz, 2H), 5.05 (d, J = 15.5 Hz, 1H), 4.91 (d, J = 15.5 Hz, 1H), 4.12 (q, J = 6.8 Hz, 2H), 3.78 (s, 3H), 3.72 (dd, J = 9.0, 5.7 Hz, 1H) 3.28-3.05 (m, 2H), 1.20 (t, J = 7.1 Hz, 3H)
2-07; δ 8.41 (dd, J = 4.8, 1.5 Hz, 1H), 8.17 (d, J = 2.4 Hz, 1H), 7.70-7.56 (m, 2H) 7.25-7.07 (m, 3H), 7.05-6.85 (m, 1H), 6.76 (t, J = 7.7 Hz, 2H), 5.11 (d, J = 15.2 Hz, 1H), 4.88 (d, J = 14.9 Hz, 1H), 4.10 (q, J = 7.1 Hz, 2H), 3.94 (t, J = 7.7 Hz, 1H) ), 3.37-3.18 (m, 2H), 1.18 (t, J = 7.1 Hz, 3H)
2-08; δ 8.45 (dd, J = 4.8, 0.6 Hz, 1H), 8.19 (d, J = 2.4 Hz, 1H), 8.08 (d, J = 2.7 Hz, 1H), 7.72 (td, J = 7.7, 2.1 Hz, 1H), 7.56 (dd, J = 8.0, 2.1 Hz, 1H), 7.40 (dd, J = 7 .9, 2, 4 Hz, 1H), 7.29-7.13 (m, 3H), 6.97 (d, J = 6.8 Hz, 1H), 5.06 (d, J = 15.2 Hz, 1H), 4.85 (d, J = 15.5 Hz, 1H), 4.12 (q, J = 7.1 Hz, 2H), 3.78 (t, J = 7.4 Hz, 1H), 3. 31-3.11 (m, 2H), 1.20 (t, J = 7.1 Hz, 3H)
2-09; δ 8.72 (d, J = 0.9 Hz, 1H), 8.45-8.33 (m, 1H), 8.26 (d, J = 2.4 Hz, 1H), 7.86 −7.74 (m, 2H), 7.65 (td, J = 7.7, 2.1 Hz, 1H), 7.30−7.22 (m, 1H), 7.19 (ddd, J = 7.4, 4.8, 0.9 Hz, 1H), 6.94 (d, J = 6.6 Hz, 1H), 5.64 (s, 1H), 5.17 (d, J = 15.5 Hz) , 1H), 5.03 (d, J = 15.5 Hz, 1H), 4.25 (q, J = 7.1 Hz, 2H), 1.25 (t, J = 7.1 Hz, 3H)
2-12; δ 8.45-8.40 (m, 1H), 8.15 (d, J = 2.4 Hz, 1H), 7.70-7.55 (m, 2H), 7.30-7 .15 (m, 3H), 7.00-6.75 (m, 3H), 5.03 (d, J = 15.0 Hz, 1H), 4.89 (d, J = 15.0 Hz, 1H) 4.15 (q, J = 7.2 Hz, 2H), 4.02 (dd, J = 8.9, 6.3 Hz, 1H), 3.35-3.20 (m, 2H), 1. 22 (t, J = 7.2Hz, 3H)
3-01; δ 8.51 (d, J = 4.8 Hz, 1H), 8.00 (s, 1H), 7.85-7.75 (m, 1H), 7.66 (ddd, J = 7 .8, 7.8, 1.8 Hz, 1H), 7.30-7.20 (m, 1H), 7.05 (d, J = 8.5 Hz, 2H), 6.90-6.75 ( m, 4H), 5.13 (d, J = 15.1 Hz, 1H), 4.89 (d, J = 15.1 Hz, 1H), 4.79 (s, 1H), 4.15 (qd, J = 7.2 Hz, 2.1 Hz, 2H), 3.77 (s, 3H), 1.22 (t, J = 6.9 Hz, 3H)
3-02; δ 8.50 (d, J = 3.0 Hz, 1H), 8.01 (d, J = 1.5 Hz, 1H), 7.81 (ddd, J = 8.4, 8.4) 2.4 Hz, 1H), 7.64 (ddd, J = 7.5, 7.5, 1.2 Hz, 1H), 7.30-7.20 (m, 1H), 6.95-6.80 (M, 2H), 6.35 (t, J = 2.1 Hz, 1H), 6.26 (d, J = 1.8 Hz, 2H), 5.10 (d, J = 15.3 Hz, 1H) 4.91 (d, J = 15.3 Hz, 1H), 4.77 (s, 1H), 4.25-4.10 (m, 2H), 3.71 (s, 6H), 1.23 (T, J = 7.2Hz, 3H)
3-04; δ 8.50 (d, J = 3.0 Hz, 1H), 8.19 (d, J = 2.4 Hz, 1H), 7.71-7.59 (m, 2H), 7.30 −7.07 (m, 3H), 7.00-6.65 (m, 4H), 5.11 (d, J = 15.3 Hz, 1H), 4.89 (d, J = 15.3 Hz, 1H), 4.83 (s, 1H), 4.15 (q, J = 6.9 Hz, 2H), 3.73 (s, 3H), 1.22 (t, J = 7.2 Hz, 3H)
3-07; δ 8.50 (dd, J = 4.8, 1.8 Hz, 1H), 8.17 (d, J = 2.4 Hz, 1H), 7.78-7.60 (m, 2H) 7.35-7.20 (m, 2H), 7.04 (d, J = 9.0 Hz, 2H), 6.95-6.75 (m, 3H), 5.12 (d, J = 15.3 Hz, 1 H), 4.92 (d, J = 15.3 Hz, 1 H), 4.82 (s, 1 H), 3.78 (s, 3 H), 2.08 (s, 3 H)
3-09; δ 8.51 (d, J = 3.6 Hz, 1H), 8.18 (d, J = 2.1 Hz, 1H), 7.70-7.60 (m, 2H), 7.23 (D, J = 9.0 Hz, 2H), 7.04 (d, J = 9.9 Hz, 2H), 7.00-6.82 (br, 1H), 6.78 (d, J = 8. 7 Hz, 2H), 5.12 (d, J = 15.0 Hz, 1H), 4.88 (d, J = 15.0 Hz, 1H), 4.80 (s, 1H), 4.15 (q, J = 9.0 Hz, 2H), 3.77 (s, 3H), 1.22 (t, J = 8.4 Hz, 3H)
3-10; δ 8.51 (d, J = 4.8 Hz, 1H), 8.18 (d, J = 2.4 Hz, 1H), 7.66 (ddd, J = 7.8, 7.8, 1.8 Hz, 2H), 7.24 (t, J = 8.7 Hz, 2H), 7.05 (d, J = 8.5 Hz, 2H), 7.00-6.80 (br, 1H), 6.79 (d, J = 8.9 Hz, 2H), 5.13 (d, J = 15.0 Hz, 1H), 4.88 (d, J = 15.0 Hz, 1H), 4.80 (s) , 1H), 4.15-3.95 (m, 2H), 3.77 (s, 3H), 1.61 (ddd, J = 14.3, 14.3, 7.2 Hz, 2H), 0 .87 (t, J = 7.5 Hz, 3H)
3-12; δ 8.54 (dd, J = 4.8, 2.1 Hz, 1H), 8.16 (d, J = 2.4 Hz, 1H), 7.83 (dd, J = 8.2) 2.4 Hz, 1H), 7.67 (ddd, J = 7.5, 7.5, 2.1 Hz, 1H), 7.30-7.20 (m, 2H), 7.09 (d, J = 8.9 Hz, 2H), 6.93 (d, J = 7.8 Hz, 1H), 6.82 (d, J = 8.5 Hz, 2H), 5.11 (s, 1H), 5.10 (D, J = 15.5 Hz, 1H), 4.90 (d, J = 15.5 Hz, 1H), 3.78 (s, 3H), 2.75 (s, 3H), 2.66 (s , 3H)
3-14; δ 8.50 (d, J = 3.0 Hz, 1H), 8.18 (d, J = 2.4 Hz, 1H), 7.72-7.62 (m, 2H), 7.32 −7.20 (m, 2H), 7.01 (d, J = 9.0 Hz, 2H), 6.88 (brs, 1H), 6.76 (d, J = 8.7 Hz, 2H), 5 .12 (d, J = 15.0 Hz, 1H), 4.88 (d, J = 15.0 Hz, 1H), 4.78 (s, 1H), 4.50 (sep, J = 6.0 Hz, 1H), 4.22-4.05 (m, 2H), 1.31 (d, J = 6.0 Hz, 6H), 1.22 (t, J = 7.2 Hz, 3H)
3-15; δ 8.50 (d, J = 3.0 Hz, 1H), 8.17 (d, J = 2.4 Hz, 1H), 7.68-7.61 (m, 2H), 7.30 −7.18 (m, 2H), 7.05 (d, J = 8.7 Hz, 2H), 7.00-6.85 (m, 3H), 5.14 (s, 2H), 5.12 (D, J = 14.4 Hz, 1H), 4.87 (d, J = 15.3 Hz, 1H), 4.79 (s, 1H), 4.22-4.08 (m, 2H), 3 .47 (s, 3H), 1.22 (t, J = 7.2 Hz, 3H)
3-16; δ 8.50 (dd, J = 5.1, 1.8 Hz, 1H), 8.19 (d, J = 2.4 Hz, 1H), 7.72-7.65 (m, 2H) 7.27-7.22 (m, 2H), 7.14 (d, J = 8.7 Hz, 2H), 6.97 (dd, J = 6.6, 1.8 Hz, 2H), 6. 88 (brs, 1H), 5.14 (d, J = 15.0 Hz, 1H), 4.88 (s, 1H), 4.84 (d, J = 15.0 Hz, 1H), 4.22- 4.09 (m, 2H), 2.28 (s, 3H), 1.22 (t, J = 7.2 Hz, 3H)
3-17; δ 8.50 (dd, J = 4.8, 0.9 Hz, 1H), 8.19 (d, J = 2.4 Hz, 1H), 7.75-7.63 (m, 2H) , 7.32-7.22 (m, 4H), 7.16 (d, J = 9.0 Hz, 2H), 6.92 (d, J = 7.5 Hz, 1H), 5.18 (d, J = 15.6 Hz, 1H), 4.93 (s, 1H), 4.80 (d, J = 15.6 Hz, 1H), 4.24-4.07 (m, 2H), 1.22 ( t, J = 7.2 Hz, 3H)
3-18; δ 8.51 (dd, J = 4.5, 1.2 Hz, 1H), 8.20 (d, J = 2.1 Hz, 1H), 7.78-7.65 (m, 2H) 7.40-7.15 (m, 6H), 6.92 (d, J = 7.2 Hz, 1H), 5.19 (d, J = 15.3 Hz, 1H), 4.93 (s, 1H), 4.81 (d, J = 15.3 Hz, 1H), 4.30-4.10 (m, 2H), 1.22 (t, J = 7.2 Hz, 3H)
3-19; δ 8.51 (d, J = 4.4 Hz, 1H), 8.18 (d, J = 2.4 Hz, 1H), 7.75-7.60 (m, 2H), 7.30 −7.20 (m, 2H), 6.89 (s, 1H), 6.95-6.80 (br, 1H), 6.70 (s, 2H), 5.12 (d, J = 15) .5Hz, 1H), 4.90 (d, J = 15.3 Hz, 1H), 4.78 (s, 1H), 4.25-4.05 (m, 2H), 2.23 (s, 6H) ), 1.30-1.15 (m, 3H)
3-20; δ 8.50 (d, J = 3.0 Hz, 1H), 8.19 (d, J = 3.0 Hz, 1H), 7.72-7.62 (m, 2H), 7.27 −7.20 (m, 2H), 6.89 (brs, 1H), 6.35 (t, J = 2.1 Hz, 1H), 6.26 (d, J = 2.1 Hz, 2H), 5 .10 (d, J = 15.0 Hz, 1H), 4.91 (d, J = 15.0 Hz, 1H), 4.78 (s, 1H), 4.25-4.10 (m, 2H) 3.71 (s, 6H), 1.23 (t, J = 7.2 Hz, 3H)
3-21; δ 8.27 (d, J = 4.5 Hz, 1H), 8.15 (d, J = 2.4 Hz, 1H), 7.67 (d, J = 7.5 Hz, 1H), 7 .45-7.19 (m, 3H), 6.97 (d, J = 8.1 Hz, 2H), 6.74 (d, J = 8.7 Hz, 2H), 5.14 (d, J = 15.3 Hz, 1 H), 4.72 (d, J = 15.3 Hz, 1 H), 4.67 (s, 1 H), 4.14 (q, J = 7.2 Hz, 2 H), 3.76 ( s, 3H), 1.23 (t, J = 7.2 Hz, 3H)
3-23; δ 8.40 (d, J = 4.7 Hz, 1H), 8.30-8.10 (br, 1H), 7.77 (dd, J = 8.3, 2.5 Hz, 1H) 7.70-7.45 (br, 1H), 7.30-7.20 (m, 3H), 6.95-6.65 (br, 3H), 5.50-4.00 (br, 3H), 3.76 (s, 3H), 3.20-2.10 (br, 9H)
3-24; δ 8.39 (d, J = 4.7 Hz, 1H), 8.16 (brs, 1H), 7.79 (dd, J = 8.1, 2.3 Hz, 1H), 7.75 -7.45 (br, 1H), 7.30-7.20 (m, 3H), 6.95-6.65 (br, 3H), 5.50-4.00 (br, 3H), 3 .76 (s, 3H), 3.50-2.50 (br, 4H), 2.40-2.00 (br, 3H), 1.90-1.30 (m, 4H)
3-25; δ 8.35 (brs, 1H), 8.15 (brs, 1H), 7.90-7.40 (br, 2H), 7.39-7.15 (m, 2H), 6. 86 (brs, 1H), 6.56 (brs, 2H), 5.20-4.00 (br, 5H), 2.28 (brs, 6H), 2.10-1.45 (br, 3H) , 1.35-1.10 (m, 3H)
3-26; δ 8.37 (d, J = 4.5 Hz, 1H), 8.18 (d, J = 2.2 Hz, 1H),
7.69 (d, J = 7.5 Hz, 1H), 7.25 (t, J = 7.5 Hz, 1H), 7.20-7.00 (m, 3H), 6.80 (d, J = 8.5 Hz, 2H), 6.65 (brs, 1H), 5.08 (d, J = 15.1 Hz, 1H), 4.88 (d, J = 15.1 Hz, 1H), 4.74. (S, 1H), 4.14 (q, J = 7.2 Hz, 2H), 3.78 (s, 3H), 2.28 (s, 3H), 1.22 (t, J = 7.2 Hz) , 3H)
3-27; δ 8.32 (s, 1H), 8.15 (d, J = 2.1 Hz, 1H), 7.66 (d, J = 6.3 Hz, 1H), 7.44 (dd, J = 8.1, 2.4 Hz, 1H), 7.21 (d, J = 8.1 Hz, 1H), 7.06 (d, J = 8.7 Hz, 2H), 6.85-6.70 ( m, 3H), 5.08 (d, J = 15.3 Hz, 1H), 4.84 (d, J = 15.3 Hz, 1H), 4.73 (s, 1H), 4.14 (q, J = 6.9 Hz, 2H), 3.77 (s, 3H), 2.35 (s, 3H), 1.21 (t, J = 6.9 Hz, 3H)
3-28; δ 8.20 (d, J = 2.4 Hz, 1H), 7.67 (dd, J = 8.1, 2.4 Hz, 1H), 7.53 (t, J = 7.8 Hz, 1H), 7.21 (d, J = 8.1 Hz, 1H), 7.13-7.02 (m, 3H), 6.85-6.75 (m, 2H), 6.75-6. 65 (br, 1H), 5.10 (d, J = 15.0 Hz, 1H), 4.85 (d, J = 15.0 Hz, 1H), 4.78 (s, 1H), 4.14 ( q, J = 6.9 Hz, 2H), 3.78 (s, 3H), 2.16 (s, 3H), 1.21 (t, J = 6.9 Hz, 3H)
3-30; δ 8.51 (d, J = 4.2 Hz, 1H), 8.19 (d, J = 2.1 Hz, 1H), 7.75-7.61 (m, 2H), 7.52 (D, J = 8.1 Hz, 2H), 7.35-7.20 (m, 4H), 7.00-6.85 (br, 1H), 5.17 (d, J = 15.3 Hz, 1H), 4.93 (s, 1H), 4.84 (d, J = 15.3 Hz, 1H), 4.25-4.07 (m, 2H), 1.22 (d, J = 7. 2Hz, 3H)
3-31; δ 8.46 (d, J = 3.6 Hz, 1H), 8.21 (d, J = 2.4 Hz, 1H), 7.75-7.58 (m, 2H), 7.25 -7.15 (m, 2H), 7.03-6.85 (m, 2H), 6.80-6.62 (m, 2H), 5.28 (s, 1H), 5.10 (d , J = 15.9 Hz, 1H), 4.97 (d, J = 15.3 Hz, 1H), 4.30-4.10 (m, 2H), 3.73 (s, 3H), 3.51. (S, 3H), 1.24 (d, J = 7.2 Hz, 3H)
3-32; δ 8.51 (dd, J = 4.8, 1.2 Hz, 1H), 8.20 (d, J = 2.1 Hz, 1H), 7.75-7.60 (m, 2H) , 7.32-7.18 (m, 2H), 6.89 (brs, 1H), 6.80-6.68 (m, 2H), 6.62-6.50 (m, 1H), 5 .10 (d, J = 15.0 Hz, 1H), 4.90 (d, J = 15.0 Hz, 1H), 4.79 (s, 1H), 4.28-4.10 (m, 2H) , 3.84 (s, 3H), 3.80 (s, 3H), 1.23 (d, J = 7.2 Hz, 3H)
3-34; δ 8.52 (dd, J = 4.7, 1.0 Hz, 1H), 8.20-8.05 (m, 2H), 7.69 (ddd, J = 7.8, 7. 8, 1.9 Hz, 1 H), 7.59 (dd, J = 8.2, 2.4 Hz, 1 H), 7.35-7.25 (m, 1 H), 7.22 (d, J = 8 .2 Hz, 1H), 7.08 (d, J = 8.5 Hz, 2H), 6.90-6.75 (m, 3H), 5.00 (d, J = 2.4 Hz, 2H), 4 .58 (s, 1H), 4.00-3.80 (m, 2H), 3.77 (s, 3H)
3-38; δ 8.46 (d, J = 5.0 Hz, 1H), 8.20 (d, J = 2.5 Hz, 1H), 7.80-7.65 (m, 3H), 7.49 (D, J = 8.5 Hz, 1H), 7.37 (d, J = 8.5 Hz, 1H), 7.30-7.20 (m, 2H), 7.00-6.90 (brs, 1H), 5.19 (s, 1H), 5.13 (d, J = 15.4 Hz, 1H), 4.94 (d, J = 15.4 Hz, 1H), 4.20 (q, J = 7.2 Hz, 2H), 1.22 (t, J = 7.2 Hz, 3H)
3-44; δ 8.52 (dd, J = 4.8, 1.2 Hz, 1H), 8.17 (d, J = 2.4 Hz, 1H), 7.74-7.62 (m, 2H) 7.28-6.84 (m, 7H), 5.10 (d, J = 15.3 Hz, 1H), 4.95 (s, 1H), 4.92 (d, J = 15.3 Hz, 1H), 2.87-2.72 (m, 2H), 2.29 (s, 3H), 1.60-1.45 (m, 2H), 0.90 (t, J = 7.2 Hz, 3H)
3-47; δ 8.49 (d, J = 4.8 Hz, 1H), 8.21 (d, J = 2.5 Hz, 1H), 7.89 (d, J = 6.5 Hz, 1H), 7 .71 (dd, J = 7.8, 7.8 Hz, 1H), 7.70 (dd, J = 7.7, 7.7 Hz, 1H), 7.60-7.50 (m, 1H), 7.30-7.20 (m, 2H), 7.06 (dd, J = 8.9, 8.9 Hz, 1H), 7.00-6.90 (brs, 1H), 5.26 (s , 1H), 5.17 (d, J = 15.4 Hz, 1H), 4.90 (d, J = 15.4 Hz, 1H), 4.20 (q, J = 7.2 Hz, 2H), 1 .24 (t, J = 7.2 Hz, 3H)
3-49; δ 8.49 (d, J = 4.7 Hz, 1H), 8.22 (d, J = 2.5 Hz, 1H), 7.75-7.65 (m, 2H), 7.52 (Dd, J = 7.4, 7.4Jz, 1H), 7.30-7.20 (m, 2H), 7.00-6.90 (brs, 1H), 6.95-6.80 ( m, 1H), 6.75-6.60 (m, 1H), 5.17 (d, J = 15.4 Hz, 1H), 5.15 (s, 1H), 4.88 (d, J = 15.4 Hz, 1H), 4.30-4.10 (m, 2H), 1.23 (t, J = 7.2 Hz, 3H)
3-50; δ 8.50 (d, J = 4.8 Hz, 1H), 8.18 (d, J = 2.4 Hz, 1H), 7.71-7.60 (m, 2H), 7.21 (D, J = 7.5 Hz, 2H), 7.12-6.97 (m, 4H), 6.90 (brs, 1H), 5.10 (d, J = 15.3 Hz, 1H), 4 .90 (d, J = 15.3 Hz, 1H), 4.81 (s, 1H), 4.10 (q, J = 7.8 Hz, 2H), 1.21 (t, J = 7.5 Hz, 3H)
3-51; δ 8.51 (d, J = 4.8 Hz, 1H), 8.18 (d, J = 2.4 Hz, 1H), 7.75-7.60 (m, 2H), 7.33 −7.20 (m, 2H), 7.18−7.02 (m, 2H), 7.00-6.80 (m, 3H), 5.12 (d, J = 15.3 Hz, 1H) , 4.87 (d, J = 15.3 Hz, 1H), 4.82 (s, 1H), 4.25-4.10 (m, 2H), 2.27 (s, 3H), 1.22 (T, J = 7.5Hz, 3H)
3-52; δ 8.48 (dd, J = 4.8, 1.2 Hz, 1H), 8.17 (d, J = 2.4 Hz, 1H), 7.71 (d, J = 6.3 Hz, 1H), 7.57 (ddd, J = 7.3, 7.3, 1.8 Hz, 1H), 7.37-7.33 (m, 1H), 7.23-7.15 (m, 4H) ), 7.03-6.97 (m, 1H), 6.76 (brs, 1H), 5.13 (d, J = 15.3 Hz, 1H), 5.03 (s, 1H), 4. 88 (d, J = 15.3 Hz, 1H), 4.25-4.10 (m, 2H), 1.22 (t, J = 7.5 Hz, 3H)
4-01; δ 8.53 (d, J = 6.6 Hz, 1H), 7.67 (ddd, J = 7.5, 7.5, 1.5 Hz, 1H), 7.32-7.24 ( m, 2H), 7.14 (t, J = 8.1 Hz, 1H), 6.95-6.85 (br, 1H), 6.79 (d, J = 8.1 Hz, 1H), 6. 71 (s, 1H), 6.63 (d, J = 7.5 Hz, 1H), 5.04 (s, 2H) 4.82 (s, 1H), 4.35-4.08 (m, 2H) ), 3.75 (s, 3H), 1.23 (t, J = 7.2 Hz, 3H)
4-02; δ 8.53 (d, J = 6.6 Hz, 1H), 7.67 (dd, J = 8.1, 2.1 Hz, 1H), 7.32-7.24 (m, 2H) 7.04 (d, J = 9.0 Hz, 2H), 7.00-6.85 (brs, 1H), 6.77 (d, J = 8.7 Hz, 2H), 5.03 (s, 2H), 4.78 (s, 1H), 4.35-4.08 (m, 2H), 3.77 (s, 3H), 1.22 (t, J = 7.2 Hz, 3H)
4-03; δ 8.52 (d, J = 6.9 Hz, 1H), 7.65 (ddd, J = 7.5, 7.5, 1.5 Hz, 1H), 7.35-7.20 ( m, 2H), 6.87 (s, 2H), 6.68 (s, 2H), 5.03 (s, 2H), 4.75 (s, 1H), 4.35-4.08 (m , 2H), 2.22 (s, 6H), 1.23 (t, J = 7.2 Hz, 3H)
4-04; δ 8.53 (dd, J = 4.8, 1.5 Hz, 1H), 7.66 (ddd, J = 7.8, 7.8, 2.1 Hz, 1H), 7.30− 7.23 (m, 2H), 6.90 (brs, 1H), 6.34 (t, J = 2.4 Hz, 1H), 6.26-6.10 (m, 2H), 5.07 ( d, J = 15.9 Hz, 1H), 4.98 (d, J = 15.9 Hz, 1H), 4.76 (s, 1H), 4.26-4.09 (m, 2H), 3. 71 (s, 6H), 1.23 (t, J = 7.2 Hz, 3H)
4-05; δ 8.49-8.27 (br, 1H), 7.80-7.42 (br, 1H), 7.38-7.22 (m, 1H), 7.20 (s, 1H) ), 6.98-6.82 (m, 2H), 6.80-6.67 (m, 2H), 5.21-4.05 (br, 5H), 3.76 (s, 3H), 2.37-2.10 (br, 1H), 1.70-1.45 (br, 2H), 1.30-1.14 (m, 3H)
4-06; δ 8.45-8.30 (br, 2H), 7.75-7.35 (br, 1H), 7.21 (s, 1H), 6.86 (brs, 1H), 6. 55 (brs, 2H), 5.30-4.80 (br, 1H), 4.55-4.05 (br, 4H), 2.19 (s, 9H), 1.30-1.15 ( br, 3H)
4-07; δ 8.40 (brs, 1H), 7.80-7.35 (br, 1H), 7.35-7.15 (br, 2H), 6.86 (brs, 1H), 6. 53 (br, 2H), 5.30-4.80 (br, 1H), 4.70-4.20 (br, 2H), 3.85-3.60 (br, 3H), 2.40- 2.10 (br, 9H)
4-12; δ 8.54 (dd, J = 4.8, 0.9 Hz, 1H), 8.32 (d, J = 2.1 Hz, 1H), 7.89 (td, J = 8.4, 3.3 Hz, 1H), 7.74 (td, J = 7.8, 1.8 Hz, 1H), 7.35-7.25 (m, 4H), 7.05-6.96 (m, 3H) ), 5.07 (d, J = 15.6 Hz, 1H), 5.02 (d, J = 15.6 Hz, 1H), 4.95 (s, 1H), 4.28-4.12 (m , 2H), 1.25 (t, J = 7.2 Hz, 3H)
4-14; δ 8.58 (dd, J = 4.8, 1.2 Hz, 1H), 8.37 (d, J = 2.4 Hz, 1H), 7.96-7.89 (m, 1H) 7.77 (td, J = 7.8, 2.1 Hz, 1H), 7.43 (t, J = 1.5 Hz, 1H), 7.38-7.28 (m, 3H), 7. 11 (s, 1H), 7.04 (dd, J = 7.8, 2.4 Hz, 2H), 5.09 (s, 1H), 5.05 (s, 2H), 2.92-2. 77 (m, 2H), 1.62-1.48 (m, 2H), 0.91 (t, J = 7.5 Hz, 3H)
4-19; δ 8.58-8.52 (m, 1H), 7.75-7.67 (m, 1H), 7.35-7.21 (m, 2H), 7.02-6.90 (M, 1H), 6.84-6.70 (m, 3H), 5.07 (d, J = 15.3 Hz, 1H), 5.00 (d, J = 15.3 Hz, 1H), 4 .91 (s, 1H), 2.88-2.70 (m, 2H), 2.29 (s, 3H), 1.60-1.45 (m, 2H), 0.91 (t, J = 7.8Hz, 3H)
4-20; δ 8.56 (dd, J = 4.8, 0.9 Hz, 1H), 7.67 (td, J = 7.8, 1.8 Hz, 1H), 7.32-7.25 ( m, 2H), 7.17 (t, J = 7.8 Hz, 1H), 7.00-6.85 (br, 1H), 6.85-6.78 (m, 2H), 6.71 ( d, J = 7.5 Hz, 1H), 5.08 (d, J = 15.6 Hz, 1H), 5.02 (d, J = 15.6 Hz, 1H), 4.92 (s, 1H), 3.76 (s, 3H), 2.25 (s, 3H)
4-21; δ 8.56 (dd, J = 4.8, 0.9 Hz, 1H), 7.68 (td, J = 7.8, 1.8 Hz, 1H), 7.32-7.25 ( m, 2H), 7.17 (t, J = 7.8 Hz, 1H), 7.00-6.88 (br, 1H), 6.85-6.78 (m, 2H), 6.72 ( d, J = 7.5 Hz, 1H), 5.07 (d, J = 17.4 Hz, 1H), 5.02 (d, J = 16.2 Hz, 1H), 4.92 (s, 1H), 3.76 (s, 3H), 2.89-2.72 (m, 2H), 1.61-1.46 (m, 2H), 0.91 (t, J = 7.5 Hz, 3H)
4-22; δ 8.56 (d, J = 5.1 Hz, 1H), 7.69 (td, J = 7.8, 1.8 Hz, 1H), 7.33-7.25 (m, 2H) 7.18 (t, J = 7.8 Hz, 1H), 7.00-6.88 (br, 1H), 6.87-6.78 (m, 2H), 6.72 (d, J = 7.5 Hz, 1 H), 5.08 (d, J = 15.6 Hz, 1 H), 5.02 (d, J = 15.6 Hz, 1 H), 4.89 (s, 1 H), 3.77 ( s, 3H), 3.66-3.52 (m, 1H), 1.23 (d, J = 6.9 Hz, 6H)
4-23; δ 8.56 (dd, J = 4.8, 0.9 Hz, 1H), 7.68 (td, J = 7.8, 1.8 Hz, 1H), 7.32-7.25 ( m, 2H), 7.15 (t, J = 7.8 Hz, 1H), 7.00-6.88 (br, 1H), 6.85-6.78 (m, 2H), 6.72 ( d, J = 7.5 Hz, 1H), 5.05 (s, 2H), 4.92 (s, 1H), 3.77 (s, 3H), 2.83 (t, J = 7.8 Hz, 2H), 1.55-1.40 (m, 2H), 1.38-1.25 (m, 2H), 0.87 (t, J = 6.9 Hz, 3H)
4-24; δ 8.55 (d, J = 4.8, 1.2 Hz, 1H), 7.68 (td, J = 7.8, 1.8 Hz, 1H), 7.32-7.25 ( m, 2H), 7.17 (t, J = 7.8 Hz, 1H), 7.00-6.87 (br, 1H), 6.85-6.76 (m, 2H), 6.71 ( d, J = 7.5 Hz, 1H), 5.08 (d, J = 15.6 Hz, 1H), 5.01 (d, J = 15.6 Hz, 1H), 4.87 (s, 1H), 3.77 (s, 3H), 1.39 (s, 9H)
4-25; δ 8.55 (dd, J = 4.8, 0.9 Hz, 1H), 7.68 (td, J = 7.8, 1.8 Hz, 1H), 7.31-7.26 ( m, 2H), 7.17 (t, J = 7.8 Hz, 1H), 7.00-6.88 (br, 1H), 6.85-6.78 (m, 2H), 6.72 ( d, J = 7.5 Hz, 1H), 5.04 (s, 2H), 4.94 (s, 1H), 3.76 (s, 3H), 2.82-2.68 (m, 2H) , 1.82-1.65 (m, 1H), 0.90 (dd, J = 6.6, 0.9 Hz, 1H)
4-26; δ 8.55 (dd, J = 4.8, 1.2 Hz, 1H), 7.68 (td, J = 7.5, 1.8 Hz, 1H), 7.32-7.24 ( m, 2H), 7.17 (t, J = 7.8 Hz, 1H), 7.00-6.88 (br, 1H), 6.85-6.78 (m, 2H), 6.72 ( d, J = 7.5 Hz, 1H), 5.04 (s, 2H), 4.91 (s, 1H), 3.76 (s, 3H), 3.53-3.40 (m, 1H) 1.60-1.46 (m, 2H), 1.22 (dd, J = 6.9, 1.8 Hz, 3H), 0.88 (dd, J = 7.5 Hz, 3H)
4-27; δ 8.54 (dd, J = 4.8, 1.9 Hz, 1H), 7.70 (ddd, J = 8.0, 7.4, 1.9 Hz, 1H), 7.55- 7.38 (m, 3H), 7.34-7.21 (m, 3H), 6.90 (d, J = 6.9 Hz, 1H), 5.06 (d, J = 15.1 Hz, 1H) ), 4.98 (d, J = 15.1 Hz, 1H), 4.93 (s, 1H), 4.24-4.08 (m, 2H), 1.23 (t, J = 7.2 Hz) , 3H)
4-28; δ 8.56 (dd, J = 4.8, 1.9 Hz, 1H), 7.73 (ddd, J = 7.7, 7.4, 1.9 Hz, 1H), 7.58− 7.51 (m, 2H), 7.43 (dd, J = 7.7, 7.4 Hz, 1H), 7.37-7.29 (m, 3H), 6.96 (d, J = 7 .4 Hz, 1H), 5.07 (d, J = 15.1 Hz, 1H), 5.06 (s, 1H), 5.00 (d, J = 15.1 Hz, 1H), 2.87-2 .79 (m, 2H), 1.63-1.45 (m, 2H), 0.91 (t, J = 7.4 Hz, 3H)
4-29; δ 8.56 (dd, J = 4.8, 1.5 Hz, 1H), 7.83-7.74 (m, 2H), 7.72 (s, 2H), 7.39-7 .33 (m, 1H), 7.30 (s, 1H), 7.02 (d, J = 8.4 Hz, 1H), 5.18 (s, 1H), 5.07 (d, J = 15 .3 Hz, 1 H), 5.00 (d, J = 15.3 Hz, 1 H), 2.87-2.75 (m, 2 H), 1.62-1.47 (m, 2 H), 0.91 (T, J = 7.8Hz, 3H)
4-30; δ 8.55 (dd, J = 4.8, 1.2 Hz, 1H), 7.67 (td, J = 7.8, 2.1 Hz, 1H), 7.31-7.24 ( m, 2H), 6.90 (brs, 1H), 6.40-6.31 (m, 3H), 5.09 (d, J = 15.3 Hz, 1H), 5.00 (d, J = 15.6 Hz, 1H), 4.86 (s, 1H), 3.73 (s, 6H), 2.90-2.73 (m, 2H), 1.63-1.47 (m, 2H) , 0.91 (t, J = 7.2 Hz, 3H)
4-31; δ 8.56 (dd, J = 4.8, 1.2 Hz, 1H), 7.68 (td, J = 7.8, 1.8 Hz, 1H), 7.32-7.26 ( m, 2H), 7.00-6.80 (br, 1H) 6.37 (t, J = 2.4 Hz, 1H), 6.31 (d, J = 2.4 Hz, 1H), 5.09 (D, J = 15.6 Hz, 1H), 4.98 (d, J = 15.6 Hz, 1H), 4.82 (s, 1H), 3.73 (s, 6H), 1.40 (s , 9H)
4-35; δ 8.37 (d, J = 4.8 Hz, 1H), 8.10 (d, J = 8.5 Hz, 1H), 7.95-7.80 (m, 3H), 7.65 -7.32 (m, 5H), 7.25-7.15 (m, 1H), 6.96-6.60 (m, 3H), 5.81 (s, 1H), 5.04 (s , 2H), 3.75 (s, 3H)
5-01; δ 8.25 (d, J = 2.4 Hz, 1H), 7.70-7.01 (m, 6H), 6.84 (d, J = 8.4 Hz, 2H), 5.58 (D, J = 17.1 Hz, 1H), 5.34 (d, J = 17.1 Hz, 1H), 4.86 (brs, 1H), 4.17 (q, J = 7.2 Hz, 2H) , 3.77 (s, 3H), 1.23 (t, J = 7.5 Hz, 3H)
5-02; δ 8.25 (brs, 1H), 7.70-7.00 (m, 5H), 6.84 (d, J = 8.5 Hz, 2H), 5.53 (d, J = 15 .0 Hz, 1H), 5.27 (d, J = 15.0 Hz, 1H), 4.80 (brs, 1H), 4.18 (q, J = 7.2 Hz, 2H), 3.79 (s) , 3H), 2.39 (s, 3H), 1.23 (t, J = 7.2 Hz, 3H)
7-01; δ 8.48 (d, J = 4.8 Hz, 1H), 7.63 (dd, J = 9.0, 2.1 Hz, 1H), 7.30-7.15 (m, 5H) 7.05-6.95 (m, 2H), 6.75-6.55 (brs, 1H), 5.04 (d, J = 15.5 Hz, 1H), 4.94 (d, J = 15.5 Hz, 1H), 4.12 (q, J = 7.2 Hz, 2H), 3.76 (dd, J = 6.9, 6.9 Hz, 1H), 3.35-3.10 (m , 2H), 1.19 (t, J = 7.2 Hz, 3H)
7-02; δ 8.55-8.45 (br, 1H), 7.90-7.70 (br, 1H), 7.50-7.10 (m, 5H), 7.10-6.90. (M, 2H), 6.90-6.70 (br, 1H), 5.07 (d, J = 15.5 Hz, 1H), 4.81 (d, J = 15.5 Hz, 1H), 3 .90-3.70 (br, 1H), 3.45-3.10 (m, 2H)
8-01; δ 9.10 (s, 1H), 8.69 (s, 2H), 8.56 (dd, J = 4.8, 1.4 Hz, 1H), 7.75 (ddd, 7.8) , 7.7, 1.9 Hz, 1H), 7.60-7.53 (m, 2H), 7.44 (dd, J = 7.7, 7.7 Hz, 1H), 7.40-7. 27 (m, 2H), 7.01 (d, J = 7.7 Hz, 1H), 5.12 (d, J = 15.1 Hz, 1H), 5.09 (s, 1H), 4.92 ( d, J = 15.1 Hz, 1H), 2.89-2.74 (m, 2H), 1.60-1.67 (m, 2H), 0.90 (t, J = 7.4 Hz, 3H) )
9-01; δ 8.52 (dd, J = 4.2, 1.8 Hz, 1H), 8.17 (d, J = 2.4 Hz, 1H), 7.80-7.42 (m, 4H) 7.35-7.17 (m, 4H), 6.98 (d, J = 7.5 Hz, 1H), 5.00 (s, 2H), 3.68 (s, 2H)
9-03; δ 8.54 (dd, J = 4.2, 1.8 Hz, 1H), 8.17 (d, J = 2.4 Hz, 1H), 7.75-7.60 (m, 2H) 7.36 (d, J = 8.5 Hz, 2H), 7.30-7.20 (m, 2H), 7.03-6.90 (m, 3H), 5.06 (s, 2H) 3.58 (s, 2H)
9-04; δ 8.53 (d, J = 4.2 Hz, 1H), 8.17 (d, J = 2.4 Hz, 1H), 7.72-7.60 (m, 2H), 7.30 −7.20 (m, 2H), 7.12 (d, J = 8.5 Hz, 2H), 7.03-6.90 (m, 3H), 5.00 (s, 2H), 3.59 (S, 2H)
9-05; δ 8.56 (dd, J = 4.2, 1.8 Hz, 1H), 8.18 (d, J = 2.1 Hz, 1H), 7.87-7.82 (m, 2H) , 7.75 (ddd, J = 7.6, 7.6, 2.1 Hz, 1H), 7.65 (dd, J = 8.3, 2.8 Hz, 1H), 7.34-7.22. (M, 4H), 7.02 (d, J = 8.3 Hz, 1H), 4.99 (s, 2H), 3.71 (s, 2H), 3.03 (s, 3H)
9-06; δ 8.53 (dd, J = 4.2, 1.8 Hz, 1H), 8.17 (d, J = 2.4 Hz, 1H), 7.72-7.60 (m, 2H) , 7.32-7.14 (m, 4H), 7.05-6.93 (m, 3H), 5.01 (s, 2H), 3.61 (s, 2H)
9-07; δ 8.53 (d, J = 4.8 Hz, 1H), 8.20 (s, 1H), 7.75-7.60 (m, 2H), 7.30-7.10 (m , 4H), 7.05-6.90 (m, 1H), 6.80-6.71 (m, 1H), 6.67-6.60 (m, 2H), 5.00 (s, 2H) ), 3.74 (s, 3H), 3.62 (s, 2H)
9-08; δ 8.52 (d, J = 4.2 Hz, 1H), 8.18 (d, J = 2.4 Hz, 1H), 7.80-7.68 (m, 2H), 7.40. -6.90 (m, 7H), 5.04 (s, 2H), 3.65 (s, 2H)
9-09; δ 8.54 (d, J = 4.8 Hz, 1H), 8.19 (d, J = 2.4 Hz, 1H), 7.78-7.62 (m, 2H), 7.32 −7.18 (m, 2H), 6.95 (d, J = 8.4 Hz, 1H), 6.72 (d, J = 8.4 Hz, 1H), 6.62 (d, J = 2. 1 Hz, 1 H), 6.52 (dd, J = 8.4, 2.1 Hz, 1 H), 5.02 (s, 2 H), 3.84 (s, 3 H), 3.80 (s, 3 H) 3.59 (s, 2H)
9-10; δ 8.50 (dd, J = 4.8, 1.8 Hz, 1H), 8.22 (d, J = 2.4 Hz, 1H), 7.74-7.62 (m, 2H) 7.28-7.05 (m, 3H), 6.75-6.67 (m, 3H), 5.05 (s, 2H), 3.72 (s, 3H), 3.65 (s) , 3H), 3.60 (s, 2H)
9-11; δ 8.53 (d, J = 4.8 Hz, 1H), 8.16 (d, J = 2.1 Hz, 1H), 7.79-7.58 (m, 2H), 7.32 −7.20 (m, 2H), 7.13 (s, 1H), 7.05-6.90 (m, 2H), 6.78 (d, J = 8.6 Hz, 1H), 5.00 (S, 2H), 3.85 (s, 3H), 3.55 (s, 2H)
9-12; δ 8.52 (d, J = 4.8 Hz, 1H), 8.23 (d, J = 2.4 Hz, 1H), 7.73-7.65 (m, 2H), 7.27 −7.18 (m, 2H), 7.12−7.02 (m, 2H), 6.98 (s, 1H), 6.75 (d, J = 8.6 Hz, 1H), 5.05 (S, 2H), 3.64 (s, 3H), 3.62 (s, 2H)
9-13; δ 8.53 (d, J = 4.8 Hz, 1H), 8.24 (d, J = 1.8 Hz, 1H), 8.18 (d, J = 1.8 Hz, 1H), 7 .94-7.86 (m, 1H), 7.75-7.63 (m, 2H), 7.28-7.19 (m, 2H), 7.11 (dd, J = 8.3, 2.1 Hz, 1H), 7.01 (d, J = 7.5 Hz, 1H), 6.97-6.86 (m, 3H), 5.02 (s, 2H), 3.79 (s, 3H), 3.62 (s, 2H)
10-01; δ 8.55 (d, J = 4.8 Hz, 1H), 7.73 (dd, J = 7.8, 7.8 Hz, 1H), 7.35-7.20 (m, 3H) 7.19-6.90 (m, 4H), 5.06 (s, 2H), 3.64 (s, 2H)
10-02; δ 8.53 (d, J = 4.8 Hz, 1H), 7.69 (ddd, J = 7.3, 7.3, 1.8 Hz, 1H), 7.31-7.19 ( m, 4H), 7.05-6.95 (m, 3H), 5.07 (s, 2H), 3.62 (s, 2H), 1.29 (s, 9H)
10-03; δ 8.56 (d, J = 4.8 Hz, 1H), 7.73 (ddd, J = 7.3, 7.3, 1.8 Hz, 1H), 7.55-7.20 ( m, 6H), 6.99 (d, J = 7.8 Hz, 1H), 5.05 (s, 2H), 3.71 (s, 2H)
10-04; δ 8.42 (d, J = 4.8 Hz, 1H), 7.60 (d, J = 7.8 Hz, 1H), 7.35-6.97 (m, 5H), 6.85. (D, J = 7.8 Hz, 1H), 5.02 (d, J = 15.1 Hz, 1H), 4.75 (d, J = 15.1 Hz, 1H), 3.53-3.30 ( m, 2H), 2.11 (s, 3H), 2.00 (s, 3H)
10-05; δ 8.41 (d, J = 4.8 Hz, 1H), 7.57 (d, J = 7.6 Hz, 1H), 7.27 (d, J = 7.6 Hz, 1H), 7 .19 (s, 1H), 6.81 (s, 1H), 6.51 (s, 2H), 5.03 (d, J = 15.1 Hz, 1H), 4.70 (d, J = 15 .1 Hz, 1H), 3.39 (d, J = 14.4 Hz, 1H), 3.31 (d, J = 14.4 Hz, 1H), 2.20 (s, 6H), 1.91 (s) , 3H)
10-06; δ 8.54 (d, J = 4.8 Hz, 1H), 7.69 (ddd, J = 7.6, 7.6, 2.1 Hz, 1H), 7.31-7.23 ( m, 1H), 7.05-6.90 (brs, 1H), 6.45 (d, J = 2.1 Hz, 1H), 6.32-6.29 (m, 1H), 6.19 ( d, J = 2.1 Hz, 2H), 5.06 (s, 2H), 3.78 (s, 2H), 3.72 (s, 6H)
10-07; δ 8.56 (d, J = 4.8 Hz, 1H), 7.72 (ddd, J = 7.6, 7.6, 1.2 Hz, 1H), 7.33-7.27 ( m, 1H), 7.00 (d, J = 7.5 Hz, 1H), 6.85-6.62 (m, 3H), 6.65 (d, J = 7.5 Hz, 1H), 5. 05 (s, 2H), 3.59 (s, 2H), 2.26 (s, 3H)
10-08; δ 8.58 (d, J = 4.2 Hz, 1H), 8.35 (d, J = 2.1 Hz, 1H), 7.89 (ddd, J = 7.6, 7.6) 1.2 Hz, 1H), 7.76 (ddd, J = 7.6, 7.6, 1.2 Hz, 1H), 7.40-7.20 (m, 4H), 7.10-6.97. (M, 2H), 6.95 (s, 1H), 5.06 (s, 2H), 3.73 (s, 2H)
10-09; δ 8.54 (d, J = 4.2 Hz, 1H), 7.73 (ddd, J = 7.8, 7.8, 1.2 Hz, 1H), 7.30-7.23 ( m, 2H), 7.09 (t, J = 8.6 Hz, 1H), 6.65-6.50 (m, 3H), 5.06 (s, 2H), 3.76 (s, 3H) 3.59 (s, 2H)
10-10; δ 8.56 (d, J = 4.2 Hz, 1H), 7.76 (dd, J = 7.8, 7.8 Hz, 1H), 7.35-7.25 (m, 2H) 7.20-7.00 (m, 4H), 5.07 (s, 2H), 3.62 (s, 2H)
――――――――――――――――――――――――――――――――――――――――
[Table 13]
―――――――――――――――――――――――――――――――――――――――
No. logP
―――――――――――――――――――――――――――――――――――――――
1-02 3.03
1-03 3.33
2-16 2.79
2-17 2.96
3-13 3.27
3-35 3.67
3-36 3.93
3-37 3.08
3-39 3.64
3-40 3.16
3-41 3.94
3-42 3.38
3-43 3.85
3-45 1.64
3-46 3.04
3-48 3.03
3-53 3.46
3-54 3.00
3-55 3.54
3-56 3.33
3-57 4.25
3-58 4.20
3-59 4.09
3-60 3.37
3-61 1.28
3-62 2.01
4-08 4.67
4-09 3.87
4-10 3.52
4-11 5.35
4-13 3.68
4-15 4.35
4-16 5.40
4-17 4.34
4-18 3.95
4-30 4.06
4-31 4.32
4-32 4.08
4-33 3.32
4-34 3.72
5-01 3.38
5-02 3.77
6-01 4.74
―――――――――――――――――――――――――――――――――――――――
Reference Example 1: Synthesis of 2- (4-methoxyphenyl) malonic acid monoethyl ester
Step 1: Synthesis of diethyl 2- (4-methoxyphenyl) malonate
To a solution of 25.4 g of 1-iodo-4-methoxybenzene, 5.3 g of picolinic acid and 107.0 g of cesium carbonate in 100 ml of 1,4-dioxane, 17.4 g of diethyl malonate and copper iodide (monovalent) 1 g was added sequentially. The inside of the reaction vessel was replaced with nitrogen gas, and then stirred for 4 hours under heating and reflux. After completion of the reaction, the reaction mixture was cooled to 0 ° C., 12N hydrochloric acid aqueous solution was added to adjust the pH to 3, followed by extraction with diethyl ether. The obtained organic layer was 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 silica gel chromatography eluting with n-hexane-ethyl acetate (3: 1) to obtain 24.5 g of the desired product as a pale yellow liquid.
1H NMR (CDCl ₃ ) Δ 7.33 (d, J = 2.2 Hz, 2H), 6.90 (d, J = 2.2 Hz, 2H), 4.55 (s, 1H), 4.30-4.10 (m, 4H), 3.80 (s, 3H), 1.26 (t, J = 7.2 Hz, 6H)
Step 2: Synthesis of 2- (4-methoxyphenyl) malonic acid monoethyl ester
To a solution of 1.0 g of diethyl 2- (4-methoxyphenyl) malonate in 7 ml of ethanol was added 3.38 ml of 1N aqueous sodium hydroxide solution, and the mixture was stirred at room temperature for 48 hours. After completion of the reaction, the solvent was distilled off under reduced pressure. Water was added to the obtained residue, the pH was adjusted to 2 with an aqueous hydrochloric acid solution, and the mixture was extracted twice with dichloromethane. 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 0.75 g of the desired product as a colorless transparent oil.
1H NMR (CDCl ₃ ) Δ 9.10-8.10 (brs, 1H), 7.31 (d, J = 8.9 Hz, 2H), 6.89 (d, J = 8.9 Hz, 2H), 4.59 (s, 1H), 4.30-4.11 (m, 2H), 3.80 (s, 3H), 1.26 (t, J = 6.2 Hz, 3H)
Reference Example 2: Synthesis of N-[(6-chloro-3-pyridyl) methyl] -N- (3-methyl-2-pyridyl) amine
A solution of 21.0 g of 2-amino-3-methylpyridine and 19.5 g of sodium hydrogencarbonate in 40 ml of water is heated to 100 ° C., 31.4 g of 2-chloro-5- (chloromethyl) pyridine is added, and the mixture is left as it is. Stir at 0 ° C. for 2 hours. After completion of the reaction, the reaction mixture was allowed to cool to room temperature, water was added, and the mixture was extracted twice with chloroform. 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 silica gel column eluting with n-hexane-ethyl acetate (gradient 9: 1 to 1: 3) to give 8.25 g of the desired product as a yellow oil. Obtained.
1H NMR (CDCl ₃ ) Δ 8.38 (d, J = 2.4 Hz, 1H), 7.98 (d, J = 5.1 Hz, 1H), 7.67 (dd, J = 8.4, 2.4 Hz, 1H), 7.25 (d, J = 5.7 Hz, 2H), 6.61-6.52 (m, 1H), 4.69 (d, J = 5.7 Hz, 2H), 4.49 (brs, 1H) ), 2.11 (s, 3H)
Reference Example 3: Synthesis of N-[(2-chloro-5-thiazolyl) methyl] -N- (3-methyl-2-pyridyl) amine
A solution of 1.91 g of 2-amino-3-methylpyridine and 1.78 g of sodium hydrogen carbonate in 5 ml of water is heated to 100 ° C., and 4.0 g of 2-chloro-5- (chloromethyl) thiazole is added at the same temperature. For 2 hours. After completion of the reaction, the reaction mixture was allowed to cool to room temperature, water was added, and the mixture was extracted twice with chloroform. 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 silica gel column eluting with n-hexane-ethyl acetate (gradient 9: 1 to 1: 3) to obtain 930 mg of the desired product as a yellow oil. .
1H NMR (CDCl ₃ ) Δ 8.07 (d, J = 1.5 Hz, 1H), 7.42 (s, 1H), 7.25 (d, J = 7.2 Hz, 1H), 6.61 (dd, J = 7. 2, 5.1 Hz, 1H), 4.76 (d, J = 6.0 Hz, 2H), 4.54 (brs, 1H), 2.08 (s, 3H)
Reference Example 4: Synthesis of 2- (4-methoxyphenyl) -3- (methylamino) -3-oxopropanoic acid
Step 1: Synthesis of ethyl 2- (4-methoxyphenyl) -3- (methylamino) -3-oxopropanoate
To a solution of 800 mg of 2- (4-methoxyphenyl) malonic acid monoethyl ester in 5 ml of 1,2-dichloroethane, 2.97 g of benzotriazol-1-yloxytris (dimethylamino) phosphonium hexafluorophosphate and 40% (by weight) 1.56 g of an aqueous solution of methylamine was sequentially added and stirred at room temperature for 3 hours. After completion of the reaction, 15 ml of water was added to the reaction mixture and extracted with 15 ml of chloroform. 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 to 1: 9 gradient) to obtain 549 mg of the desired product as a white solid.
Melting point: 133-135 ° C
1H NMR (CDCl ₃ ) Δ 7.32 (d, J = 8.9 Hz, 2H), 6.89 (d, J = 8.9 Hz, 2H), 6.72 (brs, 1H), 4.46 (s, 1H), 4 .30-4.10 (m, 2H), 3.80 (s, 3H), 2.82 (d, J = 5.1 Hz, 3H), 1.25 (dd, J = 7.2, 7.. (2Hz, 3H)
Step 2: Synthesis of 2- (4-methoxyphenyl) -3- (methylamino) -3-oxopropanoic acid
Ethyl 2- (4-methoxyphenyl) -3- (methylamino) -3-oxopropanoate To a solution of 300 mg of ethanol 8 ml and tetrahydrofuran 4 ml was added 2.4 ml of 1M sodium hydroxide aqueous solution under ice-cooling. did. After completion of the addition, the reaction mixture was warmed to room temperature and stirred at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure. To the obtained residue, 5 ml of water was added, and 35% (by weight) aqueous hydrochloric acid was added under ice cooling to adjust the pH to 3, followed by extraction with 15 ml of chloroform. 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 used in the next step without further purification.

Reference Example 5: Synthesis of N-[(6-fluoro-3-pyridyl) methyl] -N- (2-pyridyl) amine Step 1: 1-dimethylethyl-N-[(6-fluoro-3-pyridyl) methyl Synthesis of —N-2-pyridylcarbamate 3.0 g of 2- (tert-butoxycarbonylamino) pyridine was added to 10 ml of 802 mg of 55 wt% sodium hydride (dispersed in mineral oil) under ice cooling. After stirring for 15 minutes at the same temperature. After completion of stirring, 3.5 g of 5- (bromomethyl) -2-fluoropyridine was added to the reaction mixture at the same temperature. After completion of the addition, the reaction mixture was warmed to room temperature and stirred overnight. After completion of the reaction, 50 ml of water was added to the reaction mixture 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 (9: 1) to obtain 5.13 g of the objective product as a colorless transparent liquid.
1H NMR (CDCl ₃ ) δ 8.37 (d, J = 4.8 Hz, 1H), 8.20 (s, 1H), 7.86 (ddd, J = 8.1, 8.1, 2.5 Hz, 1H), 7.75-7.60 (m, 2H), 7.02 (ddd, J = 7.8, 4.8, 1.4 Hz, 1H), 6.85 (dd, J = 8.5) , 3.1 Hz, 1H), 5.16 (s, 2H), 1.45 (s, 9H)
Step 2: Synthesis of N- (6-fluoro-3-pyridylmethyl) -N- (2-pyridyl) amine 1-dimethylethyl-N-[(6-fluoro-3-pyridyl) methyl] -N-2- To a solution of 5.13 g of pyridyl carbamate in 5 ml of dichloromethane was added 25 ml of trifluoroacetic acid under ice cooling. After completion of the addition, the reaction mixture was warmed to room temperature and stirred at room temperature for 30 minutes. At room temperature, 25 ml of trifluoroacetic acid was added again and stirred for 1 hour. After completion of the reaction, the solvent was distilled off from the reaction mixture under reduced pressure. To the obtained residue, 20 ml of chloroform was added, and an aqueous solution of 10M sodium hydroxide was added until the pH reached 10 under ice cooling, followed by extraction. The obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 3.12 g of the desired product as a white solid.
1H NMR (CDCl ₃ ) δ 8.21 (s, 1H), 8.12 (d, J = 3.8 Hz, 1H), 7.81 (ddd, J = 7.9, 7.9, 2.6 Hz, 1H), 7.42 (ddd, J = 7.2, 7.5, 1.9 Hz, 1H), 6.89 (dd, J = 8.4, 2.9 Hz, 1H), 6.63 (dd , J = 7.2, 5.1 Hz, 1H), 6.39 (d, J = 8.5 Hz, 1H), 4.81 (brs, 1H), 4.56 (d, J = 6.1 Hz, 2H)
[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. Five third-instar larvae of Niloparva lugens are released per test tube, covered with a sponge and 25 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.
Compound of the present invention: 2-02, 2-05, 2-09, 2-14, 2-17, 3-01, 3-02, 3-03, 3-04, 3-05, 3-11, 3- 15, 3-20, 3-26, 3-31, 3-32, 3-35, 3-36, 3-37, 3-39, 3-41, 3-43, 3-44, 3-46, 3-47, 3-48, 3-49, 3-50, 3-51, 3-53, 3-55, 3-57, 4-01, 4-03, 4-04, 4-09, 4- 14, 4-16, 4-18, 4-19, 4-20, 4-21, 4-22, 4-23, 4-24, 4-25, 4-26, 4-27, 4-28, 4-29, 4-30, 4-31, 6-01, 7-01, 8-01
Test Example 2 Insecticidal test against white moth 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 having a concentration of 500 ppm. Immerse kanran leaves in this solution for about 10 seconds, air dry, place in a petri dish, and release 3 third-instar larvae of Plutella xylostella per petri dish, cover them, and cover at 25 ° C. Housed in. The number of dead 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.
Compound of the present invention: 3-11, 4-12, 4-14, 4-20, 4-23, 4-24, 4-26, 4-27, 4-28, 4-29, 4-30, 4- 31
Test Example 3 Insecticidal activity against citrus blue thrips Place a wet filter paper on a styrene cup with an inner diameter of 7 cm, place a bean leaf cut into 3 cm on it, and inoculate 20 larvae of citrus thrips (Frankliniella occidentalis) per leaf did. 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). The number of dead insects after 2 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.
Compound of the present invention: 3-17, 3-44, 4-21, 4-26, 4-28, 4-29, 8-01
Test Example 4 Insecticidal test against peach peach aphid A moist absorbent cotton is laid on a glass petri dish with an inner diameter of 3 cm. 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.
Compound of the present invention: 2-01, 2-02, 2-03, 2-04, 2-07, 2-12, 2-13, 2-14, 2-15, 2-17, 3-01, 3- 03, 3-04, 3-05, 3-07, 3-08, 3-09, 3-10, 3-12, 3-13, 3-14, 3-15, 3-17, 3-18, 3-19, 3-20, 3-26, 3-27, 3-28, 3-29, 3-30, 3-32, 3-33, 3-35, 3-36, 3-37, 3- 38, 3-39, 3-40, 3-41, 3-42, 3-43, 3-44, 3-46, 3-47, 3-48, 3-49, 3-50, 3-51, 3-52, 3-53, 3-54, 3-55, 3-56, 3-57, 3-58, 3-59, 3-60, 3-61, 4-01, 4-02, 4- 03, 4-04, 4-08, 4-09, 4-10, 4-13, 4-14, 4-15, 4-16, 4-17, 4-18, 4-19, 4-20, 4-21, 4-22, 4-23, 4-24, 4-25, 4-26, 4-27, 4-28, 4-29, 4-30, 4-31, 4-33, 4- 34, 4-35, 5-01, 5-02, 6-01, 7-01, 7-02, 8-01
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 500 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.
Compound of the present invention: 2-15, 3-02, 3-05, 3-09, 3-10, 3-13, 3-14, 3-20, 3-35, 3-37, 3-39, 3- 42, 3-43, 3-44, 3-46, 3-48, 3-49, 4-01, 4-02, 4-03, 4-04, 4-09, 4-20, 4-21, 4-23, 4-26, 4-28, 4-30, 4-34
Test Example 6 Soil irrigation treatment test for brown planthopper A 10% emulsion of the compound of the present invention was diluted with tap water to prepare a chemical solution having a concentration of 500 ppm.

  10 ml of the chemical solution was irrigated on the stock soil portion of the plastic cup planted rice seedling (3 leaf stage) and left in the greenhouse. Rice 4 days after the irrigation treatment was cut out and placed in a test tube, in which five third-instar larvae of the planthopper (Nilaparvata lugens) were released per test tube, covered with a sponge and housed in a constant temperature room at 25 ° C. . 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.
Compound of the present invention: 2-01, 2-02, 2-03, 2-04, 3-03, 3-04, 3-10, 3-14, 3-22, 4-01
Test Example 7 Osmotic transfer test for goldfish A 10% emulsion of the compound of the present invention was diluted with tap water to prepare a chemical solution having a concentration of 500 ppm.
10 ml of the chemical solution was put into a test tube, and the roots of kanran (2.5 true leaf stage) were soaked. One day later, kanran leaves were cut out and placed in a petri dish, in which 5 third-instar larvae of Plutella xylostella were released per petri dish, capped, and housed in a thermostatic chamber at 25 ° C. The number of dead 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.
Compound of the present invention: 4-01, 4-04, 4-21
Test Example 8: Osmotic transfer test against brown planthopper A 10% emulsion of the compound of the present invention was diluted with tap water to prepare a chemical solution having a concentration of 20 ppm, and the roots of rice cell seedlings (two leaves) were immersed. Seven days later, the rice was cut out and placed in a test tube, in which five third-instar larvae of the green planthopper (Nilaparvata lugens) were released per test tube, covered with a sponge, and housed in a thermostatic chamber at 25 ° C. Six days after the release, the number of dead insects of the brown planthopper was examined, 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.
Compound of the present invention: 2-01, 2-02, 2-03, 2-03, 2-17, 3-02, 3-03, 3-04, 3-05, 3-15, 3-15, 3- 15, 3-31, 3-32, 3-36, 3-37, 3-37, 3-39, 3-41, 3-43, 3-44, 3-46, 3-47, 3-48, 3-49, 3-51, 3-52, 3-53, 3-55, 3-56, 4-01, 4-04, 4-09, 4-13, 4-14, 4-16, 4- 19, 4-20, 4-21, 4-22, 4-23, 4-24, 4-25, 4-26, 4-27, 4-28, 4-29, 4-30, 4-31, 4-34, 6-01, 7-01, 8-01

  The novel malonic acid amide compound in the present invention is a very useful compound exhibiting excellent pest control activity, particularly insecticidal / miticidal activity.

Claims (12)

Formula (1):

[Wherein Q represents an aromatic heterocycle represented by either Q-1 or Q-2,

R ¹ represents a C ₁ -C ₆ alkyl group optionally substituted by R ⁸ ;
R ² and ^{R 3} are each independently a hydrogen _atom, C 1 -C ₆ alkyl ^group, _C 1 -C ₆ alkyl group optionally substituted by ^{R _12,} C 3 -C ₆ cycloalkyl ^group, the ^{R 12} optionally substituted _C 3 -C ₆ cycloalkyl _group, C 2 -C ₆ alkenyl ^group, _C 2 -C ₆ alkenyl group optionally substituted by ^{R _12,} C 3 -C ₆ cycloalkenyl ^group, the ^{R 12} It represents a ring represented by any one of C ₃ -C ₆ cycloalkenyl group, or U-10 from U-1 optionally substituted,
R ⁴ is a cyano group, —CHO, —C (O) OH, —C (O) R ²⁴ , —C (O) OR ²⁴ , —C (O) SR ²⁴ , —C (O) N (R ²⁵ ) R ²⁶ , —S (O) mR ²⁴ or —P (O) (OR ²⁷ ) OR ²⁸ ;
W is a halogen _atom, C 1 -C ₆ alkyl group, a _C 1 -C ₆ alkyl group, or -OR ^6, optionally substituted by ^{R 5,} when p1 and p2 represents an integer of 2 or more, each of the W may be the same as or different from each other;
R ⁵ represents a halogen atom,
R ⁶ _represents a _C 1 -C ₆ alkyl group optionally substituted by C 1 -C ₆ alkyl group or ^{R 7,}
R ⁷ represents a halogen atom,
R ⁸ represents a ring represented by any of T-1 to T-26,
T-1 to T-26 each represent a ring represented by the following structural formula;

X is a halogen _atom, C 1 -C ₆ alkyl group, a _C 1 -C ₆ alkyl or ^{OR 10} optionally substituted by ^{R 9,} when q1, q2, q3 or q4 is an integer of 2 or more Each X may be the same as or different from each other;
R ⁹ represents a halogen atom,
R ¹⁰ _represents a _C 1 -C ₆ alkyl group optionally substituted by C 1 -C ₆ alkyl group or ^{R 11,}
R ¹¹ represents a halogen atom,
R ¹² represents a halogen atom, OR ¹³ , U-1 to U-9 or U-10,
R ¹³ _represents a _C 1 -C ₆ alkyl group optionally substituted by C 1 -C ₆ alkyl group or ^{R 14,}
R ¹⁴ represents a halogen atom,
U-1 to U-10 each represent a ring represented by the following structural formula,

Z is a cyano group, a nitro group, a hydroxyl group, a halogen _atom, C 1 -C ₆ alkyl ^group, _C 1 -C ₆ alkyl group optionally substituted by ^{R _15,} C 3 -C ₆ cycloalkyl ^group, the ^{R 15} optionally substituted cycloalkyl _group, C 2 -C ₆ alkenyl ^group, _C 2 -C ₆ alkenyl group optionally substituted by ^{R _15,} C 3 -C ₆ cycloalkenyl ^group, optionally substituted by ^{R 15} C ₃ -C ₆ cycloalkenyl _group, C 2 -C ₆ alkynyl group, V-1~V-6, -CHO , -C (O) R 16, -C (O) OH, -C (O) OR 16 ^{, -C (O) N (R} 17) R 18, -OR 16, -OC (O) R 16, -OC (O) OR 16, -OS (O) nR 16, -S (O) mR 16, ^{-N (R 17) R 18,} -SF 5 , or -C = Represents ^{R 31) R 32, r1,} r2, r3, when r4 or r5 is an integer of 2 or more, each Z may be the even or different from each other the same as each other,
Za represents a hydrogen _atom, C 1 -C ₆ alkyl ^group, _C 1 -C ₆ alkyl group, V-1 to V-3 or V-4 optionally substituted by ^{R 15,}
R ¹⁵ represents a halogen atom or -OR ¹⁹ ;
R ¹⁶ _represents a C 1 -C ₆ alkyl ^group, _C 1 -C ₆ alkyl group or a phenyl group optionally substituted by ^{R 20,}
Or R ¹⁷ and ^{R 18} each independently represent a hydrogen _atom, C 1 -C ₆ alkyl or _C 1 -C ₆ alkyl group optionally substituted by ^{R 20, or} together with ^{R 17} is ^{R 18} is in the C by ₂ -C ₆ to form an alkylene or C ₂ -C ₆ alkenylene chain, it indicates that may form a 3- to 7-membered ring together with the nitrogen atom to which they are attached,
R ¹⁹ represents a C ₁ -C ₆ alkyl group,
R ²⁰ represents a halogen atom or —OR ²¹ ;
R ²¹ represents a C ₁ -C ₆ alkyl group,
V-1 to V-6 each represent a ring represented by the following structural formula;

E is a cyano group, a halogen _atom, C 1 -C ₆ alkyl ^group, _C 1 -C ₆ alkyl group optionally substituted by ^{R _33,} C 3 -C ₆ cycloalkyl ^group, optionally substituted by ^{R 33} C _{3 to} C ₆ cycloalkyl group, —OR ²² or —S (O) mR ^35, and when t1, t2 or t3 represents an integer of 2 or more, each E may be the same as or different from each other. May be different,
R ²² _represents a _C 1 -C ₆ alkyl group optionally substituted by C 1 -C ₆ alkyl group or ^{R 23,}
R ²³ represents a halogen atom,
R ²⁴ _represents a C 1 -C ₆ alkyl ^group, _C 1 -C ₆ alkyl group or a phenyl group optionally substituted by ^{R 29,}
Or R ²⁵ and ^{R 26} each independently represent a hydrogen _atom, C 1 -C ₆ alkyl or _C 1 -C ₆ alkyl group optionally substituted by ^{R 29, or, R 25} is combined with ^{R 26} is in the C by ₂ -C ₆ to form an alkylene or C ₂ -C ₆ alkenylene chain, it indicates that may form a 3- to 7-membered ring together with the nitrogen atom to which they are attached,
Or R ²⁷ and ^{R 28,} each independently represent a hydrogen _atom, C 1 -C ₆ alkyl or _C 1 -C ₆ alkyl group optionally substituted by ^{R 29, or} together with ^{R 27} is ^{R 28} is in the C by ₂ -C ₆ to form an alkylene or C ₂ -C ₆ alkenylene chain, it indicates that may form a 5-9 membered ring together with the oxygen atom attached,
R ²⁹ represents a halogen atom or —OR ³⁰ ;
R ³⁰ represents a C ₁ -C ₆ alkyl group,
R ³¹ represents -NR ³⁶ ;
R ³² represents a C ₁ -C ₆ alkyl group or —NR ³⁷ R ³⁸ ,
R ³³ represents a halogen atom,
R ³⁴ _represents a _C 1 -C ₆ alkyl group optionally substituted by C 1 -C ₆ alkyl group or ^{R 39,}
R ³⁶ represents a hydrogen atom or OR ⁴⁰ ,
R ³⁷ and ^{R 38} are each independently hydrogen _atom, C 1 -C ₆ alkyl ^group, _C 1 -C ₆ alkyl group optionally substituted by ^{R 42, -OR 43, -C (} O) R 45, —OC (O) R ⁴⁶ or a phenyl group, or R ³⁷ together with R ³⁸ forms a C ₂ -C ₆ alkylene chain or a C ₂ -C ₆ alkenylene chain to bind nitrogen Represents that a 3- to 7-membered ring may be formed together with the atoms;
R ³⁹ represents a halogen atom,
R ⁴⁰ represents a hydrogen _{atom, C} 1 -C ₆ alkyl group optionally substituted by C 1 -C ₆ alkyl group or ^{R 41,}
R ⁴¹ represents a halogen atom,
R ⁴² represents a halogen atom or a phenyl group,
R ⁴³ represents a hydrogen _atom, C 1 -C ₆ alkyl ^group, _C 1 -C ₆ alkyl group optionally substituted by ^{R _44,} a C 2 -C ₆ alkenyl group or _C 2 -C ₆ alkynyl group,
R ⁴⁴ represents a halogen atom,
R ⁴⁵ represents a C ₁ -C ₆ alkyl group,
R ⁴⁶ represents a C ₁ -C ₆ alkyl group or a C ₃ -C ₆ cycloalkyl group,
p1 represents an integer of 0, 1, 2, 3 or 4;
p2 represents an integer of 0, 1 or 2;
q1 represents an integer of 0, 1, 2, 3 or 4;
q2 represents an integer of 0, 1 or 2,
q3 represents an integer of 0, 1, 2, 3, 4, 5, 6 or 7,
q4 represents an integer of 0, 1, 2, or 3,
q5 represents an integer of 0 or 1,
r1 represents an integer of 0, 1, 2, 3, 4 or 5;
r2 represents an integer of 0, 1, 2, 3 or 4; r3 represents an integer of 0, 1, 2, or 3;
r4 represents an integer of 0, 1 or 2,
r5 represents an integer of 0, 1, 2, 3, 4 or 5;
m represents an integer of 0, 1 or 2;
n represents an integer of 1 or 2,
t1 represents an integer of 0, 1, 2, 3, 4 or 5;
t2 represents an integer of 0, 1, 2, 3 or 4;
t3 represents an integer of 0, 1, 2, or 3. ] The malonamide compound represented by these, or its salt. However, the compound represented by Formula (2) is excluded.

R ² is a hydrogen _atom, C 1 -C ₆ alkyl ^group, _C 1 -C ₆ alkyl group optionally substituted by ^{R _12,} C 3 _{~C 6} cycloalkyl group, U-1, U-2, or U- 10
R ³ represents a hydrogen atom or a C ₁ -C ₆ alkyl group,
R ⁴ is —C (O) OH, —C (O) R ²⁴ , —C (O) OR ²⁴ , —C (O) SR ²⁴ , —C (O) N (R ²⁵ ) R ²⁶ , —S. (O) represents mR ²⁴ or -P (O) (OR ²⁷ ) OR ²⁸ ;
W represents a halogen atom or a _C 1 -C ₆ alkyl group,
R ⁸ represents a ring represented by any of T-1 to T-3 or T-4,
X represents a C ₁ -C ₆ alkyl group optionally substituted with a halogen atom or R ⁹ ;
R ¹² represents a ring represented by either U-1 or U-3,
Z is a nitro group, a hydroxyl group, a halogen _atom, C 1 -C ₆ alkyl ^group, _C 1 -C ₆ alkyl group optionally substituted by ^{R 15, V-3, V} -5, -OR 16, -OC ( ^{O) R 16, -OS (O} ) nR 16, -S (O) mR 16 or ^-N (R ¹⁷⁾ represents an ^{R 18,}
R ¹⁵ represents a halogen atom,
R ¹⁷ and R ¹⁸ each independently represent a C ₁ -C ₆ alkyl group,
E represents a halogen atom or —OR ²² ;
R ²² represents a C ₁ -C ₆ alkyl group,
R ²⁴ represents a C ₁ -C ₆ alkyl group or a phenyl group,
R ²⁵ represents a hydrogen atom or a C ₁ -C ₆ alkyl group,
R ²⁶ _is, represent a _C 1 -C ₆ alkyl group optionally substituted by C 1 -C ₆ alkyl group or ^{R 29, or, R 25} is _C 2 -C ₆ alkylene chain together with ^{R 26} Represents that a 3- to 7-membered ring may be formed together with the nitrogen atom to be bonded,
R ²⁷ and R ²⁸ each independently represent a C ₁ -C ₆ alkyl group,
R ²⁹ represents a halogen atom,
p1 represents an integer of 0 or 1,
p2 represents an integer of 0 or 1,
q1 represents an integer of 1,
q2 represents an integer of 1,
q3 represents an integer of 0;
q4 represents an integer of 0;
r1 represents an integer of 0, 1 or 2;
r2 represents an integer of 1 or 2, r5 represents an integer of 0,
t2 represents an integer of 1,
The malonic acid amide compound or a salt thereof according to claim 1, wherein t3 represents an integer of 0. Q represents an aromatic heterocycle represented by Q-1.
R ² represents a C ₁ -C ₆ alkyl group or U-1 optionally substituted with R ¹² ,
R ³ represents a hydrogen atom,
R ⁴ represents —C (O) OH, —C (O) OR ²⁴ or —C (O) SR ²⁴ ;
R ¹² represents a ring represented by U-1,
Z represents a halogen _atom, C 1 -C ₆ alkyl ^group, a _C 1 -C ₆ alkyl group or ^{-OR 16} and optionally substituted by ^{R 15,}
R ¹⁶ represents a C ₁ -C ₆ alkyl group,
R ²⁴ represents a C ₁ -C ₆ alkyl group,
The malonamide compound or a salt thereof according to claim 2, wherein p1 represents an integer of 0. Formula (3):

[Wherein Q represents an aromatic heterocycle represented by either Q-1 or Q-2,
R ¹ represents a C ₁ -C ₆ alkyl group optionally substituted by R ⁸ ;
R ² represents U-1,
R ³ represents a hydrogen atom or a C ₁ -C ₆ alkyl group,
W represents a halogen atom or a _C 1 -C ₆ alkyl group,
R ⁸ represents T-1 to T-3 or T-4,
X represents a C ₁ -C ₆ alkyl group optionally substituted with a halogen atom or R ⁹ ;
R ⁹ represents a halogen atom,
Z is a nitro group, a hydroxyl group, a halogen _atom, C 1 -C ₆ alkyl ^group, _C 1 -C ₆ alkyl group optionally substituted by ^{R 15, V-3, V} -5, -OR 16, -OC ( ^{O) R 16, -OS (O} ) nR 16, -S (O) mR 16 or ^-N (R ¹⁷⁾ represents an ^{R 18,}
R ¹⁵ represents a halogen atom,
R ¹⁶ _represents a C 1 -C ₆ alkyl ^group, _C 1 -C ₆ alkyl group or a phenyl group optionally substituted by ^{R 20,}
R ¹⁷ and R ¹⁸ each independently represent a C ₁ -C ₆ alkyl group,
R ²⁰ represents a halogen atom or OR ²¹ ;
R ²¹ represents a C ₁ -C ₆ alkyl group,
E represents a halogen atom or —OR ²² ;
R ²² represents a C ₁ -C ₆ alkyl group,
p1 represents an integer of 0 or 1,
p2 represents an integer of 0 or 1,
q1 represents an integer of 1,
q2 represents an integer of 1,
q3 represents an integer of 0;
q4 represents an integer of 0;
r1 represents an integer of 1 or 2,
m represents an integer of 0, 1 or 2;
n represents an integer of 0, 1 or 2;
t2 represents an integer of 1,
t3 represents an integer of 0. Or a salt thereof. Q represents an aromatic heterocycle represented by Q-1.
R ³ represents a hydrogen atom,
W _represents a C 1 -C ₆ alkyl group,
R ⁸ represents T-1, T-2 or T-4,
X represents a halogen atom,
Z represents a halogen _atom, C 1 -C ₆ alkyl ^group, _C 1 -C ₆ alkyl group optionally substituted by ^{R 15,} V-3, the ^{-OR 16} or -S (O) ^{mR 16,}
R ¹⁶ _represents a _C 1 -C ₆ alkyl group optionally substituted by C 1 -C ₆ alkyl group or ^{R 20,}
R ²⁰ represents a halogen atom,
E represents a halogen atom;
5. The phenylacetamide compound or a salt thereof according to claim 4, wherein m represents an integer of 0 or 2.   An agrochemical containing one or more selected from the malonic acid amide compounds and salts thereof according to claim 1 as active ingredients.   A mammalian or avian internal or ectoparasite control agent comprising, as an active ingredient, one or more selected from the malonic acid amide compounds and salts thereof according to any one of claims 1 to 5.   An insecticide or acaricide containing, as an active ingredient, one or more selected from the malonic acid amide compounds and salts thereof according to claim 1.   A seed treatment agent containing one or more selected from the malonic acid amide compounds and salts thereof according to claim 1 as active ingredients. The seed treatment agent according to claim 9, wherein the seed treatment method is immersion treatment.   The soil treatment agent which contains the 1 type (s) or 2 or more types chosen from the malonic acid amide compound and its salt of Claim 1 thru | or 5 as an active ingredient. The soil treatment agent according to claim 11, wherein the soil treatment method is soil irrigation treatment.