JP4099622B2 - Substituted aminoquinazolinone (thione) derivatives or salts thereof, intermediate compounds thereof, pest control agents, and control methods - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel substituted aminoquinazolinone (thione) derivative or a salt thereof, an intermediate compound, a pest control agent containing the derivative or a salt thereof as an active ingredient, and a control method.
[0002]
[Prior art]
JP-A-8-325239 discloses that aminoquinazolinone derivatives are useful as pest control agents.
[0003]
[Problems to be solved by the invention]
As a result of intensive studies to create a novel pest control agent, the present inventors have disclosed a compound having a substituent represented by the present invention on a phenyl group belonging to the quinazolinone ring as disclosed in JP-A-8-325239. The present invention has been completed by finding that it has an effect equal to or greater than that of a compound at a low dose, and has an excellent control effect on whitefly, which is a problem particularly in agricultural and horticultural situations.
The substituted aminoquinazolinone (thione) derivative represented by the general formula (I) of the present invention or a salt thereof, and the compound represented by the general formula (II) which is an intermediate compound for producing the compound are novel compounds. In addition, the pest control agent comprising the substituted aminoquinazolinone (thione) derivative represented by the general formula (I) or a salt thereof as an active ingredient has an excellent insecticidal effect at a low dose against various pests compared to conventional drugs. It is what has.
[0004]
[Means for Solving the Problems]
The inventors of the present invention have made extensive studies on aminoquinazolinone (thione) derivatives in order to develop a pest control agent having a lower dose and superior control effect compared to conventional insecticides and having an expanded insecticidal spectrum. As a result, a novel aminoquinazolinone (thione) derivative having a bromine atom, iodine atom, perfluoroalkyl group, perfluoroalkoxy group or the like in the quinazolinone ring or a salt thereof has extremely excellent activity as a pest control agent. It is what I found.
[0005]
The present invention relates to general formula (I)
[Chemical 3]
[Wherein R is a hydrogen atom, a hydroxyl group, a formyl group, (C ₁ -C ₁₂ ) Alkyl group, halo (C ₁ -C ₆ ) Alkyl group, hydroxy (C ₁ -C ₆ ) Alkyl group, (C ₂ -C ₆ ) Alkenyl group, (C ₂ -C ₆ ) Alkynyl group, (C ₁ -C ₆ ) Alkoxy group, halo (C ₁ -C ₆ ) Alkoxy group, (C ₁ -C ₆ ) Alkoxy (C ₁ -C _Three ) Alkyl group, (C ₁ -C ₆ Alkoxy (C ₁ -C _Three Alkoxy (C ₁ -C _Three ) Alkyl group, (C ₁ -C ₆ ) Alkylthio group, halo (C ₁ -C ₆ Alkylthio group, (C ₁ -C ₆ Alkylsulfinyl group, (C ₁ -C ₆ Alkylsulfonyl group, (C ₁ -C ₆ Alkylthio (C ₁ -C _Three Alkyl group, di (C) which may be the same or different ₁ -C ₆ Alkoxy (C ₁ -C _Three ) Alkyl group, amino (C ₁ -C ₆ ) Alkyl groups, which may be the same or different, (C ₁ -C ₆ ) Alkyl group, halo (C ₁ -C ₆ ) Alkyl group, (C ₂ -C ₆ ) Alkenyl group or (C ₂ -C ₆ ) Substituted amino (C) having 1-2 substituents selected from alkynyl groups ₁ -C ₆ ) Alkyl group, cyano (C ₁ -C ₆ ) Alkyl group, (C ₁ -C ₆ Alkylcarbonyl group,
[0006]
(C ₁ -C ₆ ) Alkoxycarbonyl group, hydroxycarbonyl (C ₁ -C _Three ) Alkyl group, (C ₁ -C ₆ Alkoxycarbonyl (C ₁ -C _Three ) Alkyl group, aminocarbonyl group, same or different, (C ₁ -C ₆ ) Alkyl group, (C ₂ -C ₆ ) Alkenyl group or (C ₂ -C ₆ A substituted aminocarbonyl group having 1 to 2 substituents selected from alkynyl groups; _Three -C ₆ Cycloalkyl (C ₁ -C _Three ) Alkyl group, phenyl (C ₁ -C _Three ) Alkyl group, which may be the same or different, halogen atom, nitro group, cyano group, (C ₁ -C ₆ ) Alkyl group, halo (C ₁ -C ₆ ) Alkyl group, (C ₁ -C ₆ ) Alkoxy group, halo (C ₁ -C ₆ ) Alkoxy group, (C ₁ -C ₆ ) Alkylthio group or halo (C ₁ -C ₆ ) Substituted phenyl having 1 to 5 substituents selected from alkylthio groups on the ring (C ₁ -C _Three ) Alkyl group, phenylcarbonyl group, which may be the same or different, halogen atom, nitro group, cyano group, (C ₁ -C ₆ ) Alkyl group, halo (C ₁ -C ₆ ) Alkyl group, (C ₁ -C ₆ ) Alkoxy group, halo (C ₁ -C ₆ ) Alkoxy group, (C ₁ -C ₆ ) Alkylthio group or halo (C ₁ -C ₆ A substituted phenylcarbonyl group having 1 to 5 substituents selected from an alkylthio group on the ring, a phenylthio group, which may be the same or different, a halogen atom, a nitro group, a cyano group, (C ₁ -C ₆ ) Alkyl group, halo (C ₁ -C ₆ ) Alkyl group, (C ₁ -C ₆ ) Alkoxy group, halo (C ₁ -C ₆ ) Alkoxy group, (C ₁ -C ₆ ) Alkylthio group or halo (C ₁ -C ₆ A substituted phenylthio group having 1-5 substituents selected from alkylthio groups on the ring;
[0007]
Phenylsulfonyl group, which may be the same or different, halogen atom, nitro group, cyano group, (C ₁ -C ₆ ) Alkyl group, halo (C ₁ -C ₆ ) Alkyl group, (C ₁ -C ₆ ) Alkoxy group, halo (C ₁ -C ₆ ) Alkoxy group, (C ₁ -C ₆ ) Alkylthio group or halo (C ₁ -C ₆ ) A substituted phenylsulfonyl group having 1 to 5 substituents selected from an alkylthio group on the ring, phenyl (C ₁ -C ₆ Alkylsulfonyl group, which may be the same or different, halogen atom, nitro group, cyano group, (C ₁ -C ₆ ) Alkyl group, halo (C ₁ -C ₆ ) Alkyl group, (C ₁ -C ₆ ) Alkoxy group, halo (C ₁ -C ₆ ) Alkoxy group, (C ₁ -C ₆ ) Alkylthio group or halo (C ₁ -C ₆ ) Substituted phenyl having 1 to 5 substituents selected from alkylthio groups on the ring (C ₁ -C ₆ Alkylsulfonyl group, phenyloxycarbonyl group, which may be the same or different, halogen atom, nitro group, cyano group, (C ₁ -C ₆ ) Alkyl group, halo (C ₁ -C ₆ ) Alkyl group, (C ₁ -C ₆ ) Alkoxy group, halo (C ₁ -C ₆ ) Alkoxy group, (C ₁ -C ₆ ) Alkylthio group or halo (C ₁ -C ₆ ) A substituted phenyloxycarbonyl group having 1 to 5 substituents selected from alkylthio groups on the ring;
[0008]
Phenyloxy (C ₁ -C _Three ) Alkyl group, which may be the same or different, halogen atom, nitro group, cyano group, (C ₁ -C ₆ ) Alkyl group, halo (C ₁ -C ₆ ) Alkyl group, (C ₁ -C ₆ ) Alkoxy group, halo (C ₁ -C ₆ ) Alkoxy group, (C ₁ -C ₆ ) Alkylthio group or halo (C ₁ -C ₆ ) Substituted phenyloxy having 1 to 5 substituents selected from alkylthio groups on the ring (C ₁ -C _Three ) Alkyl group, phenyl (C ₂ -C ₆ ) Alkenyl group, which may be the same or different, halogen atom, nitro group, cyano group, (C ₁ -C ₆ ) Alkyl group, halo (C ₁ -C ₆ ) Alkyl group, (C ₁ -C ₆ ) Alkoxy group, halo (C ₁ -C ₆ ) Alkoxy group, (C ₁ -C ₆ ) Alkylthio group, halo (C ₁ -C ₆ ) Alkylthio group or (C ₁ -C ₂ ) Substituted phenyl having 1 to 5 substituents selected from alkylenedioxy group on the ring (C ₂ -C ₆ ) Alkenyl group, phenyl (C ₂ -C ₆ ) Alkynyl group, which may be the same or different, halogen atom, nitro group, cyano group, (C ₁ -C ₆ ) Alkyl group, halo (C ₁ -C ₆ ) Alkyl group, (C ₁ -C ₆ ) Alkoxy group, halo (C ₁ -C ₆ ) Alkoxy group, (C ₁ -C ₆ ) Alkylthio group, halo (C ₁ -C ₆ ) Alkylthio group or (C ₁ -C ₂ ) Substituted phenyl having 1 to 5 substituents selected from alkylenedioxy group on the ring (C ₂ -C ₆ ) Alkynyl group,
[0009]
Phenyl (C ₂ -C _Four Alkynyl (C ₁ -C _Three ) Alkyl group, which may be the same or different, halogen atom, nitro group, cyano group, (C ₁ -C ₆ ) Alkyl group, halo (C ₁ -C ₆ ) Alkyl group, (C ₁ -C ₆ ) Alkoxy group, halo (C ₁ -C ₆ ) Alkoxy group, (C ₁ -C ₆ ) Alkylthio group, halo (C ₁ -C ₆ ) Alkylthio group or (C ₁ -C ₂ ) Substituted phenyl having 1 to 5 substituents selected from alkylenedioxy group on the ring (C ₂ -C _Four Alkynyl (C ₁ -C _Three ) Alkyl group, 1,3-dioxolan-2-yl (C ₁ -C _Three ) Alkyl group or phthalimide (C ₁ -C ₆ ) Represents an alkyl group.
R ¹ May be the same or different and each represents a 5- to 6-membered heterocyclic group having 1 to 3 heteroatoms selected from an oxygen atom, a sulfur atom or a nitrogen atom, and the heterocyclic groups may be the same or different. , Halogen atom, cyano group, (C ₁ -C ₆ ) Alkyl group, halo (C ₁ -C ₆ ) Alkyl group or (C ₁ -C ₆ ) It may have 1 to 5 substituents selected from alkoxy groups, and the nitrogen atom in the heterocyclic group may represent an N-oxide group.
Y represents an oxygen atom or a sulfur atom, and Z represents
-N = C (R ² )-
(Wherein R ² Is a hydrogen atom, (C ₁ -C ₆ ) Alkyl group or halo (C ₁ -C ₆ ) Represents an alkyl group. Or
[0010]
-N (R ^Three ) -CH (R ² )-
(Wherein R ² Is the same as above, R ^Three Is a hydrogen atom, (C ₁ -C ₆ ) Alkyl group, formyl group, (C ₁ -C _Three ) Alkylcarbonyl group or halo (C ₁ -C _Three ) Represents an alkylcarbonyl group. ).
X may be the same or different, and may be a bromine atom, an iodine atom, a hydroxyl group, a cyano group, (C ₁ -C ₆ ) Alkyl group, halo (C ₁ -C _Ten ) Alkyl group, (C ₂ -C ₆ ) Alkenyl group, halo (C ₂ -C ₆ ) Alkenyl group, (C ₂ -C ₆ ) Alkynyl group, (C ₁ -C ₆ ) Alkoxy group, halo (C ₁ -C ₆ ) Alkoxy group, (C ₁ -C ₆ ) Alkylthio group, halo (C ₁ -C ₆ Alkylthio group, (C ₁ -C ₆ ) Alkylsulfinyl group, halo (C ₁ -C ₆ Alkylsulfinyl group, (C ₁ -C ₆ ) Alkylsulfonyl group, halo (C ₁ -C ₆ ) Alkylsulfonyl group, halo (C ₁ -C ₆ Alkoxyhalo (C ₁ -C ₆ ) Alkoxy group, carboxyl group, (C ₁ -C ₆ ) Alkoxycarbonyl group, aminocarbonyl group, same or different, (C ₁ -C ₆ ) Alkyl group, (C ₂ -C ₆ ) Alkenyl group or (C ₂ -C ₆ ) A substituted aminocarbonyl group having 1 to 2 substituents selected from alkynyl groups, carboxy (C ₁ -C ₆ Alkyl group,
[0011]
(C ₁ -C ₆ Alkoxycarbonyl (C ₁ -C _Three ) Alkyl group, aminocarbonyl (C ₁ -C _Three ) Alkyl groups, which may be the same or different, (C ₁ -C ₆ ) Alkyl group, (C ₂ -C ₆ ) Alkenyl group or (C ₂ -C ₆ ) Substituted aminocarbonyl having 1-2 substituents selected from alkynyl groups (C ₁ -C _Three ) Alkyl group, sulfonic acid group, aminosulfonyl group, (C ₁ -C ₆ An alkoxysulfonyl group, which may be the same or different; ₁ -C ₆ ) Alkyl group, (C ₂ -C ₆ ) Alkenyl group or (C ₂ -C ₆ A substituted aminosulfonyl group having 1 to 2 substituents selected from an alkynyl group, a phenyl group, which may be the same or different, a halogen atom, a nitro group, a cyano group, (C ₁ -C ₆ ) Alkyl group, halo (C ₁ -C ₆ ) Alkyl group, (C ₁ -C ₆ ) Alkoxy group, halo (C ₁ -C ₆ ) Alkoxy group, (C ₁ -C ₆ ) Alkylthio group, halo (C ₁ -C ₆ Alkylthio group, (C ₁ -C ₆ An alkoxysulfonyl group or the same or different, ₁ -C ₆ ) Alkyl group, (C ₂ -C ₆ ) Alkenyl group or (C ₂ -C ₆ A substituted phenyl group having on the ring 1 to 5 substituents selected from a substituted aminosulfonyl group having 1 to 2 substituents selected from an alkynyl group;
[0012]
Phenyl (C ₁ -C _Three ) Alkyl group, which may be the same or different, halogen atom, nitro group, cyano group, (C ₁ -C ₆ ) Alkyl group, halo (C ₁ -C ₆ ) Alkyl group, (C ₁ -C ₆ ) Alkoxy group, halo (C ₁ -C ₆ ) Alkoxy group, (C ₁ -C ₆ ) Alkylthio group or halo (C ₁ -C ₆ ) Substituted phenyl having 1 to 5 substituents selected from alkylthio groups on the ring (C ₁ -C _Three ) Alkyl group, phenyloxy group, which may be the same or different, halogen atom, nitro group, cyano group, (C ₁ -C ₆ ) Alkyl group, halo (C ₁ -C ₆ ) Alkyl group, (C ₁ -C ₆ ) Alkoxy group, halo (C ₁ -C ₆ ) Alkoxy group, (C ₁ -C ₆ ) Alkylthio group or halo (C ₁ -C ₆ A phenyloxy group having 1 to 5 substituents selected from an alkylthio group on the ring, a pyridyloxy group or the same or different, a halogen atom, a nitro group, a cyano group, (C ₁ -C ₆ ) Alkyl group, halo (C ₁ -C ₆ ) Alkyl group, (C ₁ -C ₆ ) Alkoxy group, halo (C ₁ -C ₆ ) Alkoxy group, (C ₁ -C ₆ ) Alkylthio group or halo (C ₁ -C ₆ ) Represents a substituted pyridyloxy group having one or more substituents selected from alkylthio groups, and n represents an integer of 0-4. ]
The substituted aminoquinazolinone (thione) derivative represented by these, its salts, and the pest control agent and control method which contain this derivative or its salts as an active ingredient.
[0013]
The present invention also relates to a general formula (II) which is an intermediate compound of a substituted aminoquinazolinone (thione) derivative represented by the general formula (I)
[Formula 4]
[Wherein X may be the same or different, bromine atom, iodine atom, hydroxyl group, cyano group, (C ₁ -C ₆ ) Alkyl group, halo (C ₁ -C _Ten ) Alkyl group, (C ₂ -C ₆ ) Alkenyl group, halo (C ₁ -C ₆ ) Alkenyl group, (C ₂ -C ₆ ) Alkynyl group, (C ₁ -C ₆ ) Alkoxy group, halo (C ₁ -C ₆ ) Alkoxy group, (C ₁ -C ₆ ) Alkylthio group, halo (C ₁ -C ₆ Alkylthio group, (C ₁ -C ₆ ) Alkylsulfinyl group, halo (C ₁ -C ₆ Alkylsulfinyl group, (C ₁ -C ₆ ) Alkylsulfonyl group, halo (C ₁ -C ₆ ) Alkylsulfonyl group, halo (C ₁ -C ₆ Alkoxyhalo (C ₁ -C ₆ ) Alkoxy group, carboxyl group, (C ₁ -C ₆ ) Alkoxycarbonyl group, aminocarbonyl group, same or different, (C ₁ -C ₆ ) Alkyl group, (C ₂ -C ₆ ) Alkenyl group or (C ₂ -C ₆ A substituted aminocarbonyl group having 1-2 substituents selected from alkynyl groups;
[0014]
Carboxy (C ₁ -C ₆ ) Alkyl group, (C ₁ -C ₆ Alkoxycarbonyl (C ₁ -C _Three ) Alkyl group, aminocarbonyl (C ₁ -C _Three ) Alkyl groups, which may be the same or different, (C ₁ -C ₆ ) Alkyl group, (C ₂ -C ₆ ) Alkenyl group or (C ₂ -C ₆ ) Substituted aminocarbonyl having 1-2 substituents selected from alkynyl groups (C ₁ -C _Three ) Alkyl group, sulfonic acid group, (C ₁ -C ₆ ) Alkoxysulfonyl group, hydrogen atom on nitrogen atom, (C ₁ -C ₆ ) Alkyl group, (C ₂ -C ₆ ) Alkenyl group or (C ₂ -C ₆ A sulfonic acid amide group having an alkynyl group, a phenyl group, which may be the same or different, a halogen atom, a nitro group, a cyano group, (C ₁ -C ₆ ) Alkyl group, halo (C ₁ -C ₆ ) Alkyl group, (C ₁ -C ₆ ) Alkoxy group, halo (C ₁ -C ₆ ) Alkoxy group, (C ₁ -C ₆ ) Alkylthio group or halo (C ₁ -C ₆ ) A substituted phenyl group having 1 to 5 substituents selected from alkylthio groups on the ring, phenyl (C ₁ -C _Three ) Alkyl group, which may be the same or different, halogen atom, nitro group, cyano group, (C ₁ -C ₆ ) Alkyl group, halo (C ₁ -C ₆ ) Alkyl group, (C ₁ -C ₆ ) Alkoxy group, halo (C ₁ -C ₆ ) Alkoxy group, (C ₁ -C ₆ ) Alkylthio group or halo (C ₁ -C ₆ ) Substituted phenyl having 1 to 5 substituents selected from alkylthio groups on the ring (C ₁ -C _Three ) Alkyl group, phenyloxy group,
[0015]
It may be the same or different, and is a halogen atom, nitro group, cyano group, ₁ -C ₆ ) Alkyl group, halo (C ₁ -C ₆ ) Alkyl group, (C ₁ -C ₆ ) Alkoxy group, halo (C ₁ -C ₆ ) Alkoxy group, (C ₁ -C ₆ ) Alkylthio group or halo (C ₁ -C ₆ A substituted phenyloxy group having 1 to 5 substituents selected from an alkylthio group on the ring, a pyridyloxy group or the same or different, a halogen atom, a nitro group, a cyano group, (C ₁ -C ₆ ) Alkyl group, halo (C ₁ -C ₆ ) Alkyl group, (C ₁ -C ₆ ) Alkoxy group, halo (C ₁ -C ₆ ) Alkoxy group, (C ₁ -C ₆ ) Alkylthio group or halo (C ₁ -C ₆ ) Represents a substituted pyridyloxy group having one or more substituents selected from alkylthio groups on the ring, n represents an integer of 0 to 4, and Y represents an oxygen atom or a sulfur atom. ]
It is related with the compound represented by these.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
In the definition of each substituent in the substituted aminoquinazolinone (thione) derivative represented by the general formula (I) of the present invention or a salt thereof, “halogen atom” means a chlorine atom, a bromine atom, an iodine atom or a fluorine atom, For example, “C ₁ -C ₁₂ ] Means 1 to 12 carbon atoms, and "(C ₁ -C ₁₂ ) "Alkyl group" means a linear or branched alkyl group having 1 to 12 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s An alkyl group such as -butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, etc. ₁ -C _Ten ) Alkyl group ”may be the same or different and represents a linear or branched alkyl group having 1 to 10 carbon atoms substituted with one or more halogen atoms, such as trifluoromethyl group, pentafluoro Indicates ethyl group, heptafluoropropyl group, etc. ₂ -C ₆ ") Alkenyl group" means a straight-chain or branched alkenyl group having 2 to 6 carbon atoms having one or more double bonds; ₂ -C ₆ ) Alkenyl group "may be the same or different, and represents a linear or branched alkenyl group having 2 to 6 carbon atoms substituted with one or more halogen atoms, and" (C ₂ -C ₆ ) "Alkynyl group" means a linear or branched alkynyl group having 2 to 6 carbon atoms having one or more triple bonds,
[0017]
『Halo (C ₂ -C ₆ ) Alkynyl group ”may be the same or different, and represents a linear or branched alkynyl group having 2 to 6 carbon atoms substituted with one or more halogen atoms,“ may be the same or different, Examples of the “5- to 6-membered heterocycle having one or more heteroatoms selected from an oxygen atom, a sulfur atom, a nitrogen atom, or a nitrogen atom” include furan, thiophene, pyrrole, oxazole, thiazole, pyrazole, imidazole, and 1,2. , 3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,2,4-triazole, pyridine, pyridazine, pyrimidine, pyrazine, pyrrolidine, piperidine, morpholine , Thiomorpholine, dithiolane, dithiane, piperazine, dioxolane, imidazolidine or tetrahydrofurane Denote the 5-6 membered heterocyclic ring and the like.
[0018]
As preferred substituents in the substituted aminoquinazolinone (thione) derivative represented by the general formula (I), R is a hydrogen atom, a formyl group, (C ₁ -C ₆ ) Alkyl group, (C ₂ -C ₆ ) Alkenyl group, (C ₂ -C ₆ ) Alkynyl group, (C ₁ -C ₆ Alkylcarbonyl group, (C ₁ -C ₆ Alkoxycarbonyl group, (C ₁ -C ₆ ) Alkylthio group, halo (C ₁ -C ₆ ) Alkylthio group, phenylcarbonyl group, substituted phenylcarbonyl group, substituted phenyl (C ₁ -C ₆ ) Alkyl group, substituted phenyl (C ₂ -C ₆ ) Alkenyl group or substituted phenyl (C ₂ -C ₆ ) Alkynyl group, R ¹ Is a pyridyl group, especially a 3-pyridyl group, Y is an oxygen atom or a sulfur atom, and Z is
-N (R ^Three ) -CH (R ² )-
And R ² And R ^Three Is a hydrogen atom or (C ₁ -C ₆ ) Alkyl group, X is bromine atom, iodine atom, halo (C ₁ -C ₆ ) Alkyl group, halo (C ₁ -C ₆ ) Alkoxy group, halo (C ₁ -C ₆ ) Alkylthio group, halo (C ₁ -C ₆ ) Alkylsulfinyl group, halo (C ₁ -C ₆ ) An alkylsulfonyl group or a phenyl group, and n is preferably an integer of 0-2.
Examples of salts of substituted aminoquinazolinone (thione) derivatives represented by the general formula (I) include salts of alkali metal atoms such as sodium and potassium in addition to mineral acid salts such as hydrochloric acid, sulfuric acid and nitric acid. can do.
[0019]
The compound represented by the general formula (II) which is an intermediate compound of the substituted aminoquinazolinone (thione) derivative represented by the general formula (I) of the present invention can be produced, for example, by the production method shown below.
Manufacturing method 1.
[Chemical formula 5]
(Wherein X and n are the same as above, R ^Four Is (C ₁ -C ₆ ) Represents an alkyl group, and Hal represents a halogen atom. )
[0020]
The compound represented by the general formula (II-1) can be produced by reacting the compound represented by the general formula (III) with hydrazine hydrate in the presence of an inert solvent. The inert solvent that can be used in this reaction is not particularly limited as long as it does not significantly inhibit the progress of this reaction. For example, alcohols such as methanol, ethanol, propanol, and butanol, and halogenated hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride. , Aromatic hydrocarbons such as benzene, toluene, xylene and monochlorobenzene, nitriles such as acetonitrile and benzonitrile, cellsolves such as methyl cellosolve, ethers such as diethyl ether, diglyme, dioxane and tetrahydrofuran, dimethylformamide , Dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, amides such as 1-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, water, and other inert solvents. Solvent is simple In or as a mixture of two or more can be used.
[0021]
The reaction temperature may be appropriately determined in the range of room temperature to the boiling point of the inert solvent used, and is preferably in the range of room temperature to 90 ° C.
Since this reaction is an equimolar reaction, the compound represented by the general formula (III) and the hydrazine hydrate may be used in an equimolar amount, but any one of the reactants can be used in excess, and preferably embraced. It is better to use water hydrazines in excess.
The reaction time is not constant depending on the reaction scale, reaction temperature, etc., but is in the range of several minutes to 48 hours.
After completion of the reaction, the target product can be produced by treating from the reaction system containing the target product by a conventional method and purifying by recrystallization, dry column chromatography or the like as necessary.
The compound represented by the general formula (III) can be produced according to Collect. Czech. Chem. Commn. (Vol. 55), 752 (1990).
[0022]
Manufacturing method 2.
[Chemical 6]
(Wherein R ^Four , X, n and Y are the same as above. )
[0023]
2-1. General formula (VIII) → General formula (VI)
A compound represented by general formula (VI) is produced by reacting a compound represented by general formula (VIII) with a compound represented by general formula (VII) in the presence of an inert solvent and a catalyst. be able to.
As the inert solvent that can be used in this reaction, for example, the inert solvents exemplified in Production Method 1 can be used, and these inert solvents can be used alone or in admixture of two or more. As the catalyst, for example, acetic acid, paratoluenesulfonic acid and the like can be used in addition to inorganic acids such as hydrochloric acid and sulfuric acid, and the amount used is 0.001% by weight with respect to the compound represented by the general formula (VIII). An amount in the range of 10% to 10% may be present in the reaction system.
[0024]
Since this reaction is an equimolar reaction, the compound represented by the general formula (VIII) and the compound represented by the general formula (VII) may be used in equimolar amounts, but any one of the reactants should be used in excess. You can also. The reaction temperature may be appropriately determined in the range of room temperature to the boiling point of the inert solvent used, and is preferably in the range of room temperature to 90 ° C. The reaction time is not constant depending on the reaction scale, reaction temperature, etc., but is in the range of several minutes to 48 hours.
After completion of the reaction, the target product can be produced from the reaction system containing the target product in the same manner as in Production Method 1.
The compound represented by the general formula (VIII) may be commercially available, and can also be produced by nitration of a substituted benzaldehyde. It can also be produced by the method described in Journal of Chemical Society 1927, 2375-2378.
[0025]
2-2. General formula (VI) → General formula (V)
A compound represented by the general formula (V) is produced by reacting the compound represented by the general formula (VI) with a reducing agent in the presence or absence of an inert solvent or by catalytic reduction. Can do.
As a reducing agent in this reduction reaction, for example, NaBH _Three CN, LiBH _Three Metal hydrides such as CN, BH _Three The amount of the reducing agent can be appropriately selected from the range of equimolar to excess molar in terms of the number of moles of hydride of the reducing agent with respect to the compound represented by the general formula (VI). And use it.
The inert solvent that can be used in this reaction is not particularly limited as long as it does not significantly inhibit the progress of this reaction.For example, alcohols such as methanol, ethanol, propanol, and butanol, cellsolves such as methyl cellosolve, diethyl ether, diglyme, Ethers such as dioxane, tetrahydrofuran, esters such as ethyl acetate, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, amides such as 1-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, An inert solvent such as water can be exemplified, and these inert solvents can be used alone or in admixture of two or more.
[0026]
This reaction is carried out under acidic to neutral conditions in the range of pH 1 to 7, preferably in the range of pH 4 to 6. The pH can be adjusted by adding hydrogen chloride, hydrogen bromide, etc. to the reaction system. It ’s fine. The reaction temperature is selected from the range of 0 ° C. to the boiling point range of the solvent, preferably in the range of room temperature to 70 ° C. The reaction time is not constant depending on the reaction scale, reaction temperature, etc., but is in the range of several minutes to 48 hours.
After completion of the reaction, the target product can be produced from the reaction system containing the target product in the same manner as in Production Method 1.
Next, when catalytic reduction is performed as a reduction reaction, for example, a method described in “Shin Experimental Chemistry Course” (Vol. 15-II: Maruzen) or the like may be used. For example, usable inert solvents include methanol, ethanol, and propanol. , Alcohols such as butanol, cellsolves such as methyl cellosolve, ethers such as diethyl ether, diglyme, dioxane and tetrahydrofuran, hydrocarbons such as hexane and cyclohexane, fatty acids such as acetic acid and ethyl acetate, or esters thereof, dimethyl Examples include formamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, amides such as 1-methyl-2-pyrrolidone, and ureas such as tetramethylurea, and these inert solvents are used alone. Or a mixture of two or more.
[0027]
Examples of the catalyst used in the reduction reaction include typical catalytic reduction catalysts such as palladium carbon, palladium black, platinum dioxide, Raney nickel, and the amount used is a compound represented by the general formula (VI). May be selected from the range of 0.1% molar equivalent to 5% molar equivalent, and preferably in the range of 0.5% molar equivalent to 1% molar equivalent. The hydrogen pressure of this reaction is in the range of normal pressure to 300 atm, and preferably in the range of normal pressure to 50 atm. The reaction temperature may be appropriately determined within the range of room temperature to the boiling point of the inert solvent used, and is preferably within the range of room temperature to 70 ° C.
The reaction time is not constant depending on the reaction scale, reaction temperature, etc., but is in the range of several minutes to 48 hours.
After completion of the reaction, the target product can be produced from the reaction system containing the target product in the same manner as when a reducing agent is used.
[0028]
2-3. General formula (V) → General formula (IV)
A compound represented by the general formula (V) and 1,1′-carbonylbis-1H-imidazole (CDI), alkoxycarbonyl halide, phosgene or thiophosgene in the presence of an inert solvent, in the presence or absence of a base. To produce a compound represented by the general formula (IV).
Examples of the inert solvent that can be used in this reaction include ethers such as diethyl ether, diglyme, dioxane, and tetrahydrofuran, aromatic hydrocarbons such as benzene, toluene, and xylene, water, and the like. An active solvent can be used individually or in mixture of 2 or more types. As the base, an inorganic base or an organic base can be used. For example, hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, etc. Examples thereof include inorganic bases such as carbonates, and organic bases such as triethylamine and pyridine. When CDI is used as a reactant, the reaction can also be carried out without a base.
[0029]
What is necessary is just to use the usage-amount of a base 2 times or more with respect to the compound represented by general formula (V). The reaction temperature may be appropriately determined within the range of room temperature to the boiling point of the inert solvent used, and is preferably within the range of room temperature to 100 ° C. The reaction time is not constant depending on the reaction scale, reaction temperature, etc., but is in the range of several minutes to 48 hours.
After completion of the reaction, the desired product can be produced from the reaction system containing the desired product in the same manner as in Production Method 1.
[0030]
2-4. General formula (IV) → General formula (II)
A compound represented by the general formula (II) can be produced by subjecting the compound represented by the general formula (IV) to an alkaline hydrolysis reaction in the presence of an inert solvent.
Examples of the inert solvent that can be used in this reaction include alcohols such as methanol, ethanol, propanol and butanol, aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether, diglyme, dioxane and tetrahydrofuran. Inert solvents such as water and water can be used, and these inert solvents can be used alone or in admixture of two or more.
As the base, alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, and magnesium hydroxide can be used. Also, R _Four Depending on the alkyl group, an organic acid such as trifluoroacetic acid or hydrochloric acid, or an inorganic acid can be used to carry out the reaction under acidic conditions. The reaction temperature may be appropriately determined within the range of 0 ° C. to the boiling point of the inert solvent used. The reaction time is not constant depending on the reaction scale, reaction temperature, etc., but is in the range of several minutes to 48 hours.
After completion of the reaction, the desired product can be produced from the reaction system containing the desired product in the same manner as in Production Method 1.
[0031]
Although the typical example of the compound represented with general formula (II) manufactured by manufacturing method 1 and 2 below is shown in Table 1, this invention is not limited to these.
In Tables 1, 3, and 4, “Ph” represents a phenyl group, and “Pyr” represents a pyridyl group.
[0032]
Formula (II)
[Chemical 7]
[0033]
[0034]
[0035]
[0036]
[0037]
[0038]
The NMR data of the compounds shown in Table 1 are shown in Table 2.
[0039]
[0040]
A typical production method of the aminoquinazolinone (thione) derivative represented by the general formula (I) of the present invention or a salt thereof is shown below.
Manufacturing method 3.
[Chemical 8]
(Where R, R ¹ , R ² , R ^Three , X, n, Y and Hal are the same as described above. However, R and R ^Three Excludes hydrogen atoms. )
[0041]
3-1. General formula (II) → General formula (I-1)
By reacting the compound represented by the general formula (II) with the compound represented by the general formula (X) in the presence of an inert solvent and a catalyst, an aminoquinazolinone represented by the general formula (I-1) ( Thion) derivatives can be produced.
The target product can be produced by carrying out this reaction in the same manner as in Production Method 2-1.
[0042]
3-2. General formula (I-1) → General formula (I-3)
By reacting the aminoquinazolinone (thione) derivative represented by the general formula (I-1) with the compound represented by the general formula (IX) in the presence or absence of an inert solvent and a base, the general formula ( An aminoquinazolinone (thione) derivative represented by I-3) can be produced.
[0043]
As the inert solvent that can be used in this reaction, for example, the inert solvent exemplified in Production Method 1 can be used, and as the base, an inorganic base or an organic base can be used. In addition to inorganic or organic bases of _Three ONa, C ₂ H _Five ONa, tC _Four H ₉ ONa, CH _Three OK, C ₂ H _Five OK, tC _Four H ₉ Alcolates such as OK and alkali metal hydrides such as NaH can also be used, and the amount used is equimolar to excess molar relative to the aminoquinazolinone (thione) derivative represented by the general formula (I-1). What is necessary is just to perform reaction by selecting suitably in the range.
The reaction temperature may be in the range of 0 ° C. to the boiling point of the inert solvent used, and preferably in the range of room temperature to 70 ° C. The reaction time is not constant depending on the reaction scale, reaction temperature, etc., but may be carried out in the range of several minutes to 48 hours.
After completion of the reaction, the target product can be produced from the reaction system containing the target product in the same manner as in Production Method 1.
[0044]
3-3. General formula (I-1) → General formula (I-2)
The target product can be produced by carrying out this reaction in the same manner as in 2-2.
3-4. General formula (I-2) → General formula (I-4)
By reacting the aminoquinazolinone (thione) derivative represented by the general formula (I-2) with the compound represented by the general formula (IX) in the presence or absence of an inert solvent and a base, the general formula ( An aminoquinazolinone (thione) derivative represented by I-4) can be produced.
The target product can be produced by the same reaction as 3-2.
3-5. General formula (I-4) → General formula (I-5)
By reacting an aminoquinazolinone (thione) derivative represented by the general formula (I-4) with a compound represented by the general formula (XI) in the presence or absence of an inert solvent and a base, the general formula ( An aminoquinazolinone (thione) derivative represented by I-5) can be produced.
The target product can be produced by the same reaction as 3-2.
3-6. General formula (I-3) → General formula (I-5)
The target product can be produced by carrying out this reaction in the same manner as in 2-2.
[0045]
In the following, representative examples of substituted aminoquinazolinone (thione) derivatives represented by the general formula (I) of the present invention or salts thereof are illustrated in Tables 3 and 4, but the present invention is not limited thereto. Absent.
[Chemical 9]
[0046]
[0047]
[0048]
[0049]
[0050]
[0051]
[0052]
[0053]
[0054]
[0055]
[Chemical Formula 10]
[0056]
[0057]
[0058]
[0059]
[0060]
[0061]
[0062]
[0063]
[0064]
[0065]
[0066]
[0067]
[0068]
[0069]
[0070]
[0071]
In Tables 1, 3, and 4, abbreviations indicate the following substituents.
c: alicyclic hydrocarbon group
Ph: phenyl group
Q ₁ : 2-pyridyl group
Q ₂ : 3-pyridyl group
Q _Three : 4-pyridyl group
Q _Four : 2-pyridyl-N-oxide group
Q _Five : 3-pyridyl-N-oxide group
Q ₆ : 4-pyridyl-N-oxide group
Q ₇ : Thiazol-5-yl group
Q ₈ : Furan-2-yl group
Q ₉ : 1,3-dioxolan-2-yl group
Q _Ten : Phthalimido-1-yl group
Q ₁₁ : Thiophen-2-yl group
[0072]
【Example】
Typical examples of the present invention are shown below, but the present invention is not limited thereto.
Example 1.3 Preparation of Amino-3,4-dihydro-6-trifluoromethoxy-2 (1H) -quinazolinone (Compound No. II-30)
Embedded image
2.84 g (0.01 mol) of methyl 2-chloromethyl-4-trifluoromethoxyphenylcarbamate is dissolved in 20 ml of methanol, and 5 g (0.1 mol) of hydrazine hydrate is added to the solution for 3 hours. The reaction was carried out under heating to reflux. After completion of the reaction, excess hydrazine hydrate and the solvent were distilled off from the reaction solution containing the target product under reduced pressure to obtain a crude product. The obtained crude product was recrystallized from 95% methanol to obtain 2.22 g of the desired product.
Physical properties: m. p. 181.5-184 ° C. Yield: 90%
[0073]
Example 2. Preparation of 3-amino-3,4-dihydro-6-pentafluoroethyl-2 (1H) -quinazolinone (Compound No. II-18).
Embedded image
3.18 g (0.01 mol) of methyl 2-chloromethyl-4-pentafluoroethylphenylcarbamate was dissolved in 20 ml of methanol and 5 g (0.1 mol) of hydrazine hydrate was added to the solution for 3 hours. The reaction was carried out under heating to reflux. After completion of the reaction, a crude product is obtained by distilling off excess hydrazine hydrate and the solvent from the reaction solution containing the desired product under reduced pressure, and the obtained crude product is recrystallized from 95% methanol for the purpose. 2.53 g of product was obtained.
Physical properties: m. p. 178.4-183.5 ° C. Yield: 90%
[0074]
Example 3.3 Preparation of 3- (3-pyridylmethylideneamino) -3,4-dihydro-6-trifluoromethoxy-2 (1H) quinazolinone (Compound No. 30).
Embedded image
0.62 g (2.5 mmol) 3-amino-3,4-dihydro-6-trifluoromethoxy-2 (1H) -quinazolinone, 0.27 g (2.5 mmol) nicotinic aldehyde and a drop of sulfuric acid Was added to 10 ml of methanol, and the reaction was carried out for 3 hours with heating under reflux. After completion of the reaction, crystals precipitated in the reaction system were collected by filtration and dried to obtain 0.76 g of the desired product.
Physical properties: m. p. 264.5-266.0 ° C. Yield: 93%
[0075]
Example 4. Preparation of 3- [1- (3-pyridylmethylideneamino) -3,4-dihydro-6-pentafluoroethyl-2 (1H) quinazolinone (Compound No. 18).
Embedded image
0.74 g (2.5 mmol) 3-amino-3,4-dihydro-6-pentafluoroethyl-2 (1H) quinazolinone, 0.27 g (2.5 mmol) nicotinic aldehyde and a drop of sulfuric acid. The mixture was added to 10 ml of methanol and reacted for 3 hours under heating and reflux. After completion of the reaction, crystals precipitated in the reaction system were collected by filtration and dried to obtain 0.78 g of the desired product.
Physical properties: m. p. 298.0-300.0 ° C. Yield: 84%
[0076]
Example 5. Preparation of 3- (3-pyridylmethylamino) -3,4-dihydro-6-trifluoromethoxy-2 (1H) quinazolinone (Compound No. 208).
Embedded image
3.36 g (2.5 mmol) 3- (3-pyridylmethylideneamino) -3,4-dihydro-6-trifluoromethoxy-2 (1H) quinazolinone and 0.2 g 5% palladium carbon Add to 30 ml acetic acid and add 3-4 kg / m ² Hydrogenation was carried out. After the theoretical amount of hydrogen has been absorbed, the catalyst is filtered off from the reaction solution, the solvent is distilled off under reduced pressure, and the residue is neutralized by adding a 20% aqueous sodium hydroxide solution. × 3), the extract was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure to give a crude product obtained by silica gel column chromatography ( Purification with ethyl acetate-methanol = 10: 1) gave 2.5 g of the desired product.
Physical properties: nD 1.5233 (22.6 ° C) Yield 74%
[0077]
Example 6.1 Preparation of monomethyl-3- (3-pyridylmethylamino) -3,4-dihydro-6-trifluoromethoxy-2 (1H) quinazolinone (Compound No. 289).
Embedded image
0.68 g (2.0 mmol) of 3- (3-pyridylmethylideneamino) -3,4-dihydro-6-trifluoromethoxy-2 (1H) quinazolinone was dissolved in 10 ml of dimethylformamide, 0.09 g of sodium hydride (62.4%) was added and reacted at room temperature for 30 minutes, and then 0.34 g of methyl iodide was added and reacted for 4 hours. After completion of the reaction, the reaction solution was poured into ice water, and the target product was extracted with ethyl acetate (20 ml × 3). The extract was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and then under reduced pressure. The crude product obtained by distilling off the solvent was purified by silica gel column chromatography (ethyl acetate-methanol = 10: 1) to obtain 2.5 g of the desired product.
Physical properties: nD 1.5467 (23.6 ° C) Yield 50%
[0078]
Example 7
7-1. Preparation of t-butyl 2- (5-hydroxy-2 mononitrophenylmethylidene) carbazic acid.
Embedded image
Add 3.34 g (0.02 mol) of 5-hydroxy-2-nitrobenzaldehyde and 2.64 g (0.02 mol) of t-butyl carbazic acid and a drop of sulfuric acid to 20 ml of methanol and heat for 3 hours. The reaction was carried out under reflux.
After completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated crystals were collected by filtration to obtain 5.06 g of the desired product.
¹ H-NMR [(CDCl _Three / TMS, δ value (ppm)]
1.57 (9H, s), 6.84 (1H, dd), 7.66 (1H, d), 7.94 (1H, d), 8.42 (1H, br.s),
8.46 (1H, s).
Yield: 90%
[0079]
7-2. Preparation of t-butyl 2- (5-methoxycarbonyloxy-2 mononitrophenylmethylidene) carbazic acid.
Embedded image
4.22 g (0.015 mol) of t-butyl 2- (5-hydroxy-2mononitrophenylmethylidene) carbazic acid obtained in Example 7-1 and 1.67 g (0.0165 mol) of triethylamine were obtained. Dissolved in 15 ml of tetrahydrofuran and cooled to 0 ° C. A solution prepared by dissolving 1.56 g (0.0165 mol) of methyl chloroformate in 5 ml of tetrahydrofuran was added dropwise to the solution over 15 minutes. Thereafter, the reaction was continued at room temperature for 3 hours. After completion of the reaction, the reaction solution was poured into 20 ml of water, and the target product was extracted with ethyl acetate (20 ml × 3). The extract was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and then under reduced pressure. The crude product obtained by distilling off the solvent was recrystallized from hexane-ether to obtain 4.6 g of the desired product.
¹ H-NMR [(CDCl _Three / TMS, δ value (ppm)]
1.54 (9H, s), 3.93 (3H, s), 7.33 (1H, dd), 8.06 (1H, d), 8.14 (1H, d),
8.21 (1H, br.s), 8.45 (1H, s).
Yield 90%
[0080]
7-3. Preparation of t-butyl 2- (21-amino-5-methoxycarbonyloxyphenylmethyl) carbazic acid.
Embedded image
T-Butyl 2- (5-methoxycarbonyloxy-2mononitrophenylmethylidene) carbazic acid 4.4 g (0.013 mol) obtained in Example 7-2 and 0.4 g of 5% palladium carbon 3 to 4 kg / m in 50 ml of methanol ² The catalytic reduction was performed. After the theoretical amount of hydrogen was absorbed, the catalyst was removed from the reaction solution by filtration, and the solvent was distilled off under reduced pressure to obtain 4 g of the desired product.
¹ H-NMR [(CDCl _Three / TMS, δ value (ppm)]
1.46 (9H, s), 3.87 (3H, s), 3.96 (2H, d), 4.6-5.0 (3H, br.s),
6.05 (1H, br.s), 6.6-6.7 (1H, m), 6.8-7.0 (2H, m).
Yield: quantitative
[0081]
7-4. Preparation of 3-t-butoxycarbonylamino-6-methoxycarbonyloxy-3,4-dihydro-2 (1H) quinazolinone.
Embedded image
3.1 g (0.01 mol) of t-butyl 2- (21-amino-5-methoxycarbonyloxyphenylmethyl) carbazic acid obtained in Example 7-3 and 2.6 g (0.01 mol) of 1 1'-carbonyl-bis-1H-imidazole was dissolved in 20 ml of tetrahydrofuran and reacted at room temperature for 3 hours. After completion of the reaction, the reaction solution was poured into 20 ml of water, and the target product was extracted with ethyl acetate (20 ml × 3). The extract was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and then under reduced pressure. 2.1 g of the desired product was obtained by recrystallizing the crude product obtained by distilling off the solvent with hexane-ethyl acetate.
¹ H-NMR [DMSO-d ₆ / TMS, δ value (ppm)]
1.42 (9H, s), 3.80 (3H, s), 4.81 (2H, s), 6.5-6.7 (3H, m), 9.01 (1H, s),
9.15 (1H, br.s).
Yield: 60%
[0082]
7-5. Preparation of 3-t-butoxycarbonylamino-6-hydroxy-3,4-dihydro-2 (1H) quinazolinone.
Embedded image
2.1 g (0.0062 mol) of 3-t-butoxycarbonylamino-6-methoxycarbonyloxy-3,4-dihydro-2 (1H) quinazolinone obtained in Example 7-4 and 0.64 g (0. 0063 mol) of sodium carbonate was added to 20 ml of 50% methanol, and the reaction was carried out for 3 hours with heating under reflux. After completion of the reaction, the methanol was distilled off under reduced pressure. The residue was collected by filtration and recrystallized from 95% methanol to obtain 1.3 g of the desired product.
¹ H-NMR [DMSO-d ₆ / TMS, δ value (ppm)]
1.42 (9,), 4.81 (2,), 6.5-6.7 (3H, s), 9.01 (1H, s), 9.10 (1H, s),
9.15 (1H, br.s).
Yield: 75%
[0083]
Preparation of 7-6.3-amino-6-hydroxy-3,4-dihydro-2 (1H) quinazolinone (Compound No. II-2).
Embedded image
1.3 g (0.0046 mol) of 3-t-butoxycarbonylamino-6-hydroxy-3,4-dihydro-2 (1H) quinazolinone obtained in Example 7-5 was added to 20 ml of trifluoroacetic acid, The reaction was carried out at room temperature for 3 hours. After completion of the reaction, 10 ml of methanol was added to the reaction solution, the solvent was distilled off under reduced pressure, and the resulting residue was recrystallized from methanol to obtain 0.74 g of the desired product.
¹ H-NMR [DMSO-d ₆ / TMS, δ value (ppm)]
4.95 (2H, s), 4.65 (2H, s), 6.51-6.63 (3H, m), 9.00 (1H, s), 9.60 (1H, br.s).
Yield 90%
[0084]
The pest control agent comprising the substituted aminoquinazolinone (thione) derivative represented by the general formula (I) of the present invention or a salt thereof as an active ingredient is various kinds of agricultural and forestry that harms rice plants, vegetables, fruit trees, other crops, flowers, etc. Suitable for pest control such as horticulture, stored grain pests, hygiene pests or nematodes, such as Empoasca brassicae, Nephotettix cincticeps, Nilaparvata lugens, Sogatella furcifera, Sogatella furcifera Diaphorina citri, citrus whitefly (Dialeurodes citri), Tobacco whitefly (Bemisia tabaci), whitefly (Trialeurodes vaporariorum), radish aphid (Brevicoryne brassicae), cotton aphid (Aphis gossypii), humb hop alo Myzus persicae), weevil (Ceroplastes) ceriferus), citrus scale insect (Pulvinaria aurantii), citrus scale insect (Pseudaonidia duplex),
[0085]
Pterylenchus coffeae, lob moth, lob moth, lob, and lobster sp. It has an effect. In addition, it can be said to be a highly safe insecticide with little effect on useful insects such as Bombyx mori and bee (Osmia cornifrons). Scientific names are based on the 1987 Agricultural and Forestry Animal and Insect Directory (Japan Society for Applied Animal Entomology).
[0086]
The pest control agent containing the substituted aminoquinazolinone (thione) derivative represented by the general formula (I) of the present invention or a salt thereof as an active ingredient is the above-mentioned pest that harms paddy fields, fruit trees, vegetables, other crops, flowers, etc. Or because it has a remarkable insecticidal effect against sanitary pests, paddy rice, fruit trees, vegetables, etc. before the occurrence of pests or when occurrence is confirmed, in accordance with the time when the occurrence of pests is predicted In the case of sanitary pests, the occurrence of the above-mentioned pests in a house or around a house is expected, such as crops, seeds such as flower buds, plants such as roots, stems and leaf flowers, paddy water, or soil. Although the desired effect of the insecticide of the present invention can be achieved by processing to the like, the present invention is not limited only to these embodiments.
[0087]
When the substituted aminoquinazolinone (thione) derivative represented by the general formula (I) of the present invention or a salt thereof is used as a pest control agent, it is formulated in a convenient form according to the conventional method for agricultural chemical formulations. It is common to use. That is, the substituted aminoquinazolinone (thione) derivative represented by the general formula (I) of the present invention or a salt thereof is used in an appropriate ratio together with an appropriate inert carrier or, if necessary, an auxiliary agent. It can be mixed and dissolved, separated, suspended, mixed, impregnated, adsorbed or adhered, and formulated into an appropriate dosage form such as a suspension, emulsion, liquid, wettable powder, granule, powder, tablet, etc. It ’s fine. The inert carrier that can be used in the present invention may be either solid or liquid. Examples of materials that can be used as a solid carrier include soybean flour, cereal flour, wood flour, bark flour, saw flour, and tobacco stem flour. , Walnut shell powder, bran, fiber powder, residue after extraction of plant extract, synthetic polymer such as pulverized synthetic resin, clays (eg kaolin, bentonite, acid clay), talc (eg talc, pyrophyllide etc.), Silicas (for example, diatomaceous earth, silica sand, mica, white carbon [some synthetic high-dispersion silicic acid, also called hydrous fine silicon, hydrous silicic acid, and some products contain calcium silicate as a main component]), activated carbon, sulfur powder, pumice, Firing diatomaceous earth, brick ground, fly ash, sand, inorganic mineral powders such as calcium carbonate and calcium phosphate, chemical fertilizers such as ammonium sulfate, phosphorous, ammonium nitrate, urea, and ammonium sulfate There may be mentioned compost or the like, which are used alone or in the form of a mixture of two or more.
[0088]
The material that can be used as a liquid carrier is selected from those having solvent ability itself and those capable of dispersing the active ingredient compound with the aid of an auxiliary agent without having solvent ability. The following carriers can be exemplified, but these are used singly or in the form of a mixture of two or more, such as water, alcohols (for example, methanol, ethanol, isopropanol, butanol, ethylene glycol, etc.), ketones ( For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, etc.), ethers (eg, ethyl ether, dioxane, cellosolve, dipropyl ether, tetrahydrofuran, etc.), aliphatic hydrocarbons (eg, kerosene, mineral oil, etc.), aromatic Hydrocarbons (eg benzene, true , Xylene, solvent naphtha, alkylnaphthalene, etc.), halogenated hydrocarbons (eg, dichloroethane, chloroform, carbon tetrachloride, etc.), esters (eg, ethyl acetate, diisopropylpropyl phthalate, dibutyl phthalate, dioctyl phthalate, etc.), amides (For example, dimethylformamide, diethylformamide, dimethylacetamide and the like), nitriles (for example, acetonitrile and the like), dimethylsulfoxides and the like can be mentioned.
[0089]
As other adjuvants, the following typical adjuvants can be mentioned, and these adjuvants are used depending on the purpose and are used alone, or in some cases, two or more kinds of adjuvants are used together. In some cases it is possible to use no adjuvants at all. Surfactants are used for the purpose of emulsifying, dispersing, solubilizing and / or wetting of the active ingredient compound, such as polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene higher fatty acid ester, polyoxyethylene. Examples of surfactants such as resin acid ester, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, alkylaryl sulfonate, naphthalene sulfonic acid condensate, lignin sulfonate, higher alcohol sulfate can do.
[0090]
In addition, for the purpose of stabilizing the dispersion of the active ingredient compound, adhesion and / or binding, the following auxiliary agents can be used, for example, casein, gelatin, starch, methylcellulose, carboxymethylcellulose, gum arabic, polyvinyl Adjuvants such as alcohol, pine oil, coconut oil, bentonite and lignin sulfonate can also be used. In order to improve the fluidity of the solid product, the following adjuvants can also be used, and for example, adjuvants such as waxes, stearates and alkyl phosphates can be used. As a peptizer for a suspension product, for example, auxiliary agents such as naphthalenesulfonic acid condensate and condensed phosphate can be used. As the antifoaming agent, for example, an auxiliary agent such as silicone oil can be used. The blending ratio of the active ingredient compound can be adjusted as necessary. For example, 0.01 to 50% by weight in the case of powder or granule, and 0.01 to 50 in the case of emulsion or wettable powder. Weight percent is appropriate.
[0091]
The pest control agent comprising the substituted aminoquinazolinone (thione) derivative represented by the general formula (I) of the present invention or a salt thereof as an active ingredient is diluted as it is or appropriately with water or the like in order to control various pests. Alternatively, an amount effective for pest control in a suspended form may be applied to the pest or a place where generation or growth of the pest is not preferable. The amount of the pesticide containing the substituted aminoquinazolinone (thione) derivative represented by the general formula (I) of the present invention or a salt thereof as an active ingredient is various factors such as the purpose, the target pest, the growth status of the crop, Although it varies depending on the occurrence tendency of pests, weather, environmental conditions, dosage form, application method, application place, application time, etc., it can be appropriately selected as an active ingredient compound from the range of 0.01 g to 5 kg per 10 ares according to the purpose. good.
[0092]
The pest control agent comprising the substituted aminoquinazolinone (thione) derivative represented by the general formula (I) of the present invention or a salt thereof as an active ingredient is further used for the control of pests to be controlled, the appropriate control period, or the dose reduction. It can be used in combination with other agricultural and horticultural insecticides, acaricides, nematicides, fungicides, biological pesticides, etc. It is also possible to use a mixture with a regulator, fertilizer and the like.
[0093]
Other agricultural and horticultural insecticides, acaricides, nematicides used for such purposes include, for example, ethione, trichlorphone, methamidophos, acephate, dichlorvos, mevinphos, monocrotophos, malathion, dimethoate, formothion, mecarbam, bamidthione, Thiometone, Disulfoton, Oxydeprophos, Nared, Methylparathion, Fenitrothion, Cyanophos, Propaphos, Fentione, Prothiophos, Profenofos, Isophenphos, Temefos, Fentoate, Dimethylvinphos, Chlorfevinphos, Tetrachlorvinphos, Hoxime, Isoxathione, Pyracrophos, Methidathion, chloropyrifos, chlorpyrifos methyl, pyridafenthion, diazinon, pyrimifosmethyl, hosalon, phosmet, di Xabenzophos, quinalphos, terbufos, ethoprophos, kazusafos, mesulfenphos, DPS (NK-0795), phosphocarb, phenamiphos, isoamidophos, phosthiazeto, isazophos, enaprophos, fenthion, phosthiethane, diclofenthion, thionadine, sulprophos, fendafothreth diphosphide ,
[0094]
Praretrin, Resmethrin, Permethrin, Tefluthrin, Bifenthrin, Fenpropatrin, Cypermethrin, Alpha cypermethrin, Cyhalothrin, Lambda cyhalothrin, Deltamethrin, Acrinatrin, Fenvalerate, Esfenvalerate, Flucitrinate, Fluverate, Et Fenprox, Halfenprox, Silafluophene, Flucitrinate, Fulvalinate, Mesomil, Oxamyl, Thiodicarb, Aldicarb, Aranicarb, Cartap, Metorcarb, Xilicarb, Propoxyl, Phenoxycarb, Fenocarb, Ethiophenecarb, Fenothiocarb, Bifenazeryl, BPMC , Carbofuran, carbosulfan, hula Ocarb, Benfuracarb, Aldoxycarb, Difenthiuron, Diflubenzuron, Teflubenzuron, Hexaflumuron, Novallon, Rufenuron, Flufenoxuron, Chlorfluazuron, Fenbutazin oxide, Tricyclohexyltin hydroxide, Sodium oleate, Potassium oleate , Metoprene, hydroprene, binapacril, amitraz,
[0095]
Zicophor, Kelsen, Chlorbenzilate, Fenisobromolate, Tetradiphone, Bensultap, Benzomate, Tebufenozide, Methoxyphenozide, Chromafenozide, Propargit, Acequinosyl, Endosulfan, Diofenolane, Chlorfenapyr, Fenpyroximate, Tolfenpyrazto, Fipronil, Tebufenepyrazto Nicotine, nitenpyram, acetamiprid, thiacloprid, imidacloprid, thiamethoxam, clothianidin, nizinotefuran, fluazinam, pyriproxyfen, hydramethylnon, pyrimidifen, pyridaben, cyromazine, TPIC (tripropylisocyanurate), pymetrozine, clofentezine, buprofe Thiocyclam, phenazaquin, quinomethionate, indoxacarb, polynactin complex, milbemectin, abamectin, emamectin benzoate, spinosad, BT (Bacillus thuringiensis), azadirachtin, rotenone, hydroxypropyl starch, levamisole hydrochloride, metam sodium, Chloronicotinyl compounds, carbamate compounds, pyrethroid compounds, macrolide compounds such as morantel tartrate, dazomet, trichlamide, bastoria, monacrosporium fimatopagum, albendazole, oxybendazole, oxfenzazole, fenbendazole Examples thereof include agricultural and horticultural insecticides, acaricides and nematicides such as organic phosphorus compounds.
[0096]
Examples of agricultural and horticultural fungicides to be used for the same purpose include sulfur, lime sulfur mixture, basic copper sulfate, iprobenphos, edifenphos, tolcrofos methyl, thiram, polycarbamate, gnebu, manzeb, mancozeb, propineb, Thiophanate, thiophanate methyl, benomyl, iminotadine acetate, iminotazine albecylate, mepronil, flutolanil, pencyclon, furamethopyl, tifluzamide, metalaxyl, oxadoxyl, carpropamide, diclofluanide, fursulfamide, chlorothalonil, crestoxime methyl, F-phenoxanil 25 (N) , Himexazole, Eclomezole, Fluorimide, Procimidone, Vinclozoline, Iprodione, Triadimephone, Triflumizole, Viterta , Triflumizole, ipconazole, fluconazole, propiconazole, difenoconazole, microbutanyl, tetraconazole, hexaconazole, tebuconazole, imibenconazole, prochloraz, pefrazoate, cyproconazole, isoprothiolane, fenarimol, pyrimethanil, mepanipyrim, pyr Phenox, fluazinam, triphorin, dichromedin, azoxystrobin, thiadiazine, captan, probenazole, acibenzofural-S-methyl (CGA-245704), fusaride, tricyclazole, pyroxylone, quinomethionate, oxolinic acid, dithianone, kasugamycin, validamycin, polyoxin, Illustrative agricultural and horticultural fungicides such as blasticidin and streptomycin Door can be,
[0097]
Similarly, herbicides include, for example, glyphosate, sulfosate, glufosinate, bialaphos, butamifos, esprocarb, prosulfocarb, beniocarb, pilibutycarb, ashram, linuron, diemron, bensulfuron-methyl, cyclosulfamuron, sinosulfuron, pyrazosulfuron ethyl , Azimusulfuron, imazosulfuron, tenylchlor, alachlor, pretilachlor, clomeprop, etobenzanide, mefenacet, pendimethalin, bifenox, acifluophene, lactofen, cihalohop-butyl, ioxonyl, bromobutide, aroxidim, cetoxidim, benzopropamide, indanopyramido Fenap, pyraflufen-ethyl, imazapyr, sulf A compound having a herbicide such as ntrazone, cfentotrol, bentoxazone, oxazoazone, paraquat, diquat, pyriminobac, simazine, atrazine, dimetamethrin, triadifram, benfrecetate, fluthiaset methyl, quizarohop ethyl, bentazone, calcium peroxide Although it can illustrate, this invention is not limited to these. The above compound names are general names except for special notes.
[0098]
Examples of biological pesticides include nuclear polyhedrosis virus (NPV), granulosis virus (GV), cytoplasmic polyhedrosis virus (CPV), insect poxvirus (Entomopox virus, EPV) ) And other virus preparations, Monocrosporium phymatophagum, Steinernema carpocapsae, Steinernema kushidai, Pasturia penetrans, etc. As microbial pesticides, Trichoderma lignorum, Agrobacterium radiobactor, non-pathogenic Erwinia carotovora, Bacillus subtilis, etc. Messenger Microbial pesticide which is, by using mixed such as biological pesticides utilized as herbicides, such as Xanthomonas campestris (Xanthomonas campestris), the same effect can be expected.
[0099]
In addition, as biological pesticides, for example, Encarsia formosa, Aphidius colemani, Aphidoletes aphidimyza, Diglyphus isaea, Dacnusa seibito mites ), Natural enemy organisms such as Amblyseius cucumeris, Orius sauteri, microbial pesticides such as Beauveria brongniartii, (Z) -10-tetradecenyl acetate, (E, Z) -4,10-tetradecadinyl acetate (Z) -8-dodecenyl acetate (Z) -11-tetradecenyl acetate (Z) -13-icosen-10-one, (Z) -8- Dodecenyl acetate (Z) -11-tetradecenyl acetate It can be used in combination with over preparative-(Z) -13-icosene-10-one-14-methyl-1-pheromone such as octadecene.
Although the typical formulation example and test example of this invention are shown below, this invention is not limited to these. In the prescription examples, “parts” means “parts by weight”.
[0100]
Formulation Example 1
50 parts of the compounds listed in Table 3 or 4
40 parts of xylene
With polyoxyethylene nonylphenyl ether
Mixture with calcium alkylbenzenesulfonate 10 parts
The above is mixed and dissolved uniformly to obtain an emulsion.
Formulation Example 2
3 parts of the compounds listed in Table 3 or 4
82 parts of clay powder
Diatomaceous earth powder 15 parts
The above is uniformly mixed and pulverized to obtain a powder.
[0101]
Formulation Example 3
5 parts of the compounds listed in Table 3 or 4
90 parts of mixed powder of bentonite and clay
5 parts calcium lignin sulfonate
The above is uniformly mixed, kneaded with an appropriate amount of water, granulated and dried to obtain granules.
Formulation Example 4
20 parts of the compounds listed in Table 3 or 4
Kaolin and synthetic highly dispersed silicic acid 75 parts
Polyoxyethylene nonylphenyl ether and al
5 parts mixture with calcium killbenzenesulfonate
The above is uniformly mixed and ground to obtain a wettable powder.
[0102]
Test Example 1 Insecticidal test against peach aphid (Myzus persicae).
Chinese cabbage was planted in plastic pots with a diameter of 8 cm and a height of 8 cm to breed peach aphids, and the number of parasites in each pot was investigated. A drug containing the compound described in Table 3 or 4 of the present invention as an active ingredient is dispersed in water and diluted to a chemical solution of 500 ppm, sprayed on the stems and leaves of potted Chinese cabbage, air-dried, and stored in a greenhouse. Then, on the 6th day after the spraying of the drug, the number of parasites of the peach aphid parasitic on each Chinese cabbage was investigated.
[0103]
Control value = 100 − {(T × Ca) / (Ta × C)} × 100
Ta: Number of parasites before treatment in the treatment area
T: Number of parasites after spraying in the treated area
Ca: Number of parasites before spraying in the untreated area
C: Number of parasites after spraying in the untreated area
Judgment criteria.
A ... Control value 100%
B ... Control value 99% ~ 90%
C ... Control value 89% -80%
D ... Control value 79% -50%
[0104]
Test Example 2 Insecticidal test against yellow planthopper (Nilaparvata lugens).
A drug containing the compound shown in Table 3 or 4 of the present invention as an active ingredient is dispersed in water and diluted in a 500 ppm chemical solution. Rice seedlings (variety: Nipponbare) are immersed in the chemical solution for 30 seconds, air-dried, and then glass. Put in a test tube, inoculate 10 each of the 3 green planthoppers, and then plug the cotton plug. After 8 days of inoculation, investigate the number of live and dead insects, calculate the death rate by the following formula, and follow the criteria of Test Example 1 Judgment was made.
[0105]
Test Example 3 Insecticidal test against Trialeuroddes vaporariorum.
Using a spray gun on a turntable against a tomato leaf in which the compound described in Table 3 or 4 of the present invention is dispersed in water and diluted to a 100 ppm chemical solution, and the chemical solution is poured into a 20 ml vial. And sprayed. After air-drying, the treated leaves were placed in a glass cylindrical tube, and 20 adults of Onshikofly lice were inoculated. After the treatment, it was placed in a greenhouse, and the number of adults was investigated 4 days after the inoculation. The death rate was calculated in the same manner as in Test Example 2, and the determination was made in the same manner as in Test Example 1.
[0106]
From the results of Test Example 1, Test Example 2 and Test Example 3, compound Nos. 6, 18, 22, 26, 30, 184, 200, 204 and 208 are excellent in A against the peach aphid of Test Example 1. In contrast to the green planthopper of Test Example 2, Compound Nos. 6, 18, 22, 26, 30, 184, 200, 204 and 208 show the excellent insecticidal effect of A, and the white fly of Test Example 3 Compound No. 6, 10, 14, 18, 22, 26, 30, 38, 78, 86, 90, 184, 200, 204 and 208 show an insecticidal effect of D or more, and in particular, compound No. 6 18, 22, 26, 30, 184, 200, 204 and 208 show the excellent insecticidal effect of A.
[0107]
【The invention's effect】
The pest control agent comprising the substituted aminoquinazolinone (thione) derivative represented by the general formula (I) of the present invention or a salt thereof as an active ingredient can be used as an onsite whitefly that does not exhibit an insecticidal effect with a compound having a similar structure. On the other hand, it exhibits an excellent insecticidal effect at a low dose, and is an excellent pest control agent as compared with the prior art.

Claims (5)

Formula (I)
[Wherein R represents a hydrogen atom, (C ₁ -C ₆ ) alkylcarbonyl group, (C ₁ -C ₆ ) alkoxycarbonyl group or phenylcarbonyl group , R ¹ represents a 3-pyridyl group , and Y represents oxygen Indicates an atom , Z is
-N = C (R ² )-( wherein R ² represents a hydrogen atom ) or
-N (R ³ ) -CH (R ² )-(wherein R ² and R ³ represent a hydrogen atom ),
X represents a 1,2,2,2-tetrafluoro-1- (trifluoromethyl) ethyl group substituted at the 6-position, and n represents an integer of 1. ]
A substituted aminoquinazolinone derivative represented by the formula: Formula (I-6)
N-acetyl-3,4-dihydro-3- (3-pyridylmethylamino) -6- [1,2,2,2-tetrafluoro-1- (trifluoromethyl) ethyl] quinazoline-2 -On. Formula (II)
[Wherein, X represents a 1,2,2,2-tetrafluoro-1- (trifluoromethyl) ethyl group substituted at the 6-position, n represents an integer of 1, and Y represents an oxygen atom. ] The compound represented by this. A pest control agent comprising the substituted aminoquinazolinone derivative according to any one of claims 1 and 2 or a salt thereof as an active ingredient. In order to control pests, the target crop or soil is treated with an effective amount of a pesticide containing the substituted aminoquinazolinone derivative or the salt thereof according to claim 1 or 2 as an active ingredient. To control pests.