JPH03128361A - Tetrahydropyrimidine compound, its production and preparation thereof - Google Patents

Abstract

PURPOSE:To obtain a safe insecticide containing a tetrahydropyrimidine compound and salt thereof, having low toxicity to human and domestic animals, fishes and natural enemies, having excellent control effect on vermins and useful for agriculture. CONSTITUTION:The objective compound containing a compound expressed by formula I (R<1> to R<4> are H, hydrocarbon or heterocycle; X is electron attracting group) and salt thereof. A compound expressed by formula II[R<1a> and R<3a> are H, hydrocarbon or heterocycle and at least one is the formula (CH2)n-R<5> (R<5> is heterocycle, etc.; (n) is 0 or 1)] contained in the compound expressed by formula I is new compound and is obtained by reacting, e.g. a compound expressed by formula III and salt thereof with an amine expressed by the formula R<4>-NH2 and salt thereof and formaldehyde. The compound expressed by formula I is preferably applied normally at an amount 0.3-3000g, preferably 50g-1000g per ha.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a tetrahydropyrimidine compound or a salt thereof useful as an insecticide, a method for producing the same, and an insecticide containing the same.

Rimei's technology A variety of synthetic compounds have been used as insecticides to control pests, but most of them are organic phosphate esters, carbamate esters, organic chlorine-containing compounds, or pyrethroid compounds. belong to.

It is well known that the frequent use of such a limited range of compounds causes harmful effects such as increased insecticide resistance in pests, which is currently a problem in various places. Furthermore, even though some of the above insecticides have high insecticidal power, they are highly toxic to humans and animals, are highly toxic to fish, are sometimes mixed with the natural enemies of pests, and are not persistent in soil, etc. The current situation is that the effects are not necessarily satisfactory for practical use, such as being too strong.

Problems to be Solved by the Invention Under the current circumstances, the present invention provides a novel insecticide that has low toxicity to humans and animals, toxicity to fish, and toxicity to natural enemies, is safe, and has an excellent control effect against pests. .

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive research for many years in order to find a new insecticide that has a completely different structure from the insecticides that have been used in the past. I have continued. As a result, the formula [wherein R', R', R3 and R4 are the same or different and represent hydrogen, an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group, and X represents an electron-withdrawing group. show. ]
It was discovered that the tetrahydropyrimidine compound represented by the formula and its salt surprisingly has a very strong insecticidal effect, and it was also found that the toxicity is low.After further studies, the present invention was completed. That is, the present invention provides (1) an insecticide characterized by containing a tetrahydropyrimidine compound [1] or a salt thereof, (2) a formula [wherein RIa, R', R'' and same 4
Taha+I11 is different from hydrogen, an optionally substituted hydrocarbon group, or an optionally substituted heterocyclic group, R
At least one of Ia and R3a has the formula -(Cu2)nR
5 (in the formula, R5 represents an optionally substituted heterocyclic group or a substituted hydrocarbon group, and n represents O or l), and X represents the same meaning as above. ] A novel tetrahydropyrimidine compound or a salt thereof, (3) a tetrahydropyrimidine compound or a salt thereof according to item (2), wherein R'' is a halogenopyridyl group or a halogenothiazolyl group, (4) a tetrahydropyrimidine The insecticide according to paragraph (1), wherein the compound or its salt is the compound according to paragraph (2) or (3), (5) formula (i) [the symbols in the formula are represented by the same meanings as above] A compound or a salt thereof is reacted with formaldehyde and an amine represented by the formula % [111] [The symbols in the formula have the same meanings as above] or a salt thereof, or (1
1) Formula [wherein R3a, R' and X have the same meanings as above, and R8 represents a lower alkyl group. ] or a salt thereof is reacted with an amine represented by the formula [the symbols in the formula have the same meanings as above] or a salt thereof, or (iii) a compound represented by the formula [
In the formula, RIb, R'', R'' and R4ai; u) (
One of them is hydrogen and the other is an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group, and X has the same meaning as above. ] or a salt thereof and the formula % [] [wherein R7 is an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group, and Y is a halogen or a halogen substituted Indicates an alkylsulfonyloxy group, an arylsulfonyloxy group, or an acyloxy group that may be substituted. A tetrahydropyrimidine compound [1a
] or a method for producing its salt.

In the above formula, R1, R1, R3, R4, R+aSR3aR
The hydrocarbon group of the "optionally substituted hydrocarbon group" represented by Ib1R1aSR3bSR4a and R7, and R
Examples of the hydrocarbon group of the "substituted hydrocarbon group" represented by 6 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, S-butyl, t-butyl,
Alkyl groups having 1 to 15 carbon atoms such as pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodenyl, tridecyl, tetradecyl, pentadecyl, etc., and 3 to 10 carbon atoms such as cyclofurovir, cyclobutyl, cyclopentyl, cyclohexyl, etc. cycloalkyls such as vinyl, allyl, 2-methylallyl, 2-
Carbon IA such as butenyl, 3-butenyl, 3-octenyl, etc.
2-10 alkenyl groups, alkynyl groups having 2-10 carbon atoms such as toehaethynyl, 2-propynyl, 3-hexynyl, etc., cycloalkenyl groups having 3-10 carbon atoms such as cyclopropenyl, cyclopentenyl, cyclohexenyl, etc. Groups with 6 to 1 carbon atoms, such as phenyl, naphthyl, etc.
0 aryl groups, such as aralkyl groups having 7 to 10 carbon atoms such as benzyl and phenylethyl.゛Also, substituents of "optionally substituted hydrocarbon group" and "
Examples of the substituents of the "substituted hydrocarbon group" include nitro, hydroxyl, oxo, thioxo, cyano, carbamoyl, carboxyl, such as methoxy! Cl-4 alkoxy-carbonyl such as J rubonyl, ethoxysulfonyl, sulfo, halokenes such as fluorine, chlorine, bromine, iodine, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, S butoxy,
Lower alkoxy having 1 to 4 carbon atoms such as t-butoxy, fenoquine, halogenophenoxy such as o-lm- or p-chlorophenoxy, o-lm- or p-bromophenoxy, such as methylthio, ethylthio, n- Lower alkylthio having 1 to 4 carbon atoms such as propylthio, isopropylthio, n-butylthio, t-butylthio, phenylthio, CI-4 such as methylsulfinyl, ethylsulfinyl, etc. Alkylsulfinyl, such as C1 such as methylsulfnyl, ethylsulfonyl, etc. -4 Alkylsulfonyl, ami/, C7-8 acylamino such as acetylamino, propionylamino, for example methylami/, ethylamino, n-propylamino, isopropylamino, n-butylamino, dimethylami/, diethylamino, cyclohexylamino, anilino Substituted amino such as C3-4 anru such as acetyl, benzoyl such as 2- or 3-thienyl, 2- or 3-furyl, 3-14- or 5-pyrazolyl, 2.4
- or 5-thiazolyl, 3-14- or 5-inchazolyl, 2-54- or 5-oxasilyl, 3-1
4- or 5-isoxacylyl, 2-14- or 5
-imidazolyl, 12.3- or 1,2.4-)riazolyl, 1[(or 2H-tetrazolyl, 2-53-
or a 5- to 6-membered heterocycle containing 1 to 4 heteroatoms selected from oxygen, sulfur, and nitrogen, such as 4-pyridyl, 2-14- or 5-pyrimidyl, 3- or 4-pyridanidyl, quinolyl, isoquinonol, indolyl, etc. groups (these heterocyclic groups are, for example, halogens such as Br, CLF, C1-4 alkyls such as methyl, ethyl, propyl, isopropyl,
0-lm- or p-chlorophenoxy, 0-lm- or p-bromophenoxy, etc. may be substituted with 1 to 4 halogenophenoxy, etc.), such as difluoromethyl, trifluoromethyl, trifluoroethyl, trichloro In addition to using 1 to 5 haloalkyl groups having 1 to 10 carbon atoms, such as ethyl, when the hydrocarbon group is aryl, aralkyl, cycloalkyl, or cycloalkenyl, alkaline groups such as those described in 2. 1 to 5 aryl, alkenyl, alkynyl, aryl, etc. may be substituted.

R1, R1, R3, R4, R+a, R:+a,
R+b*a 3b The heterocycle lλ of the "optionally substituted heterocyclic group" represented by R, RSR", R' and R7 is, for example, a hetero atom such as an oxygen atom, a sulfur atom, a nitrogen atom, etc. ~5
A 5- to 8-membered ring or a condensed ring thereof is used, and specific examples thereof include 2- or 3-thienyl,
2- or 3-furyl, 2- or 3-pyrrolyl, 2-.
3- or 4-pyridyl, 2-. 4- or 5-oxasilyl, 2-. 4- or 5-thiazolyl, 3-. 4-
or 5-pyrazolyl, 2-. 4- or 5-imitazolyl, 3-. 4- or 5-isoxacylyl.

3-14- or 5-isothiazolyl, 3- or 5-
(1,2,4-oxadiazolyl), 1,3.4oxadiazolyl, 3- or 5-(1,2,4-thiadiazolyl), 1,3,4-thiadiazolyl, 4 or 5-(
1,2,3-thiadiazolyl), l,2゜5-thiadiazolyl, l,2,3-triazolyl Il+2,4-triazolyl, IH- or 2H-tetrazolyl, N-
Oxide-2-13- or 4-pyridyl, 2-. 4-
or 5-pyrimidinyl, N-oxide-2-14- or 5-pyrimidinyl, 3- or 4-pyridazinyl,
Pyrazinyl, N-oxide-3- or 4-pyridazinyl, benzofurylbenzothiazolyl, benzoxacylyl, triazinyl, oxotriazinyl, tetracylo[
1,5-b]pyridazinyl, triazolo[4,5-b]
Pyritazinyl, oxoimidazinyl, dioxotriazinyl.

Pyrrolidinyl, piperidinyl, pyranyl, thiopyranyl, 1,4-oxazinyl, morpholinyl, 1,4-thiazinyl, 1,3-thiazinyl, piperazinyl.

Benzimidazolyl, quinolyl, inquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, intridinyl, bovine noridinyl,! , 8 naphthyridinyl, purinyl, pteridinyl, dibenzofuranyl, carbazolyl, acridinyl, phenanthridinyl, phenazinyl, phenothiazinyl.

Phenoxazinyl and the like are used. In addition, as the substituent for the "optionally substituted heterocyclic group", for example, 1 to 5 substituents selected from the substituents for the "optionally substituted hydrocarbon group" may be used. It will be done.

Preferred examples of R1, RIa and Rlb are, for example, hydrogen, CI-4 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, formula = (CII,) nHaa (
In the formula, Rsa is a 5- or 6-membered nitrogen-containing heterocyclic group optionally substituted with halogen or Ce-t.

an aryl group, n represents the same meaning as above), etc. Here, as the 5- or 6-membered nitrogen-containing heterocyclic group represented by R5a, for example, pyridyl, thiazolyl, etc. are frequently used, and as the C11-1° aryl group, for example, phenyl, etc. are often used, and these groups include, for example, chlorine,
One to three halogens such as bromine may be substituted. R
Preferred examples of ″ and R2a include hydrogen, methyl,
Cl-4 such as ethyl, propyl, isopropyl, butyl
an alkyl group, a CI-4 acyl group such as formyl, etc.
Particularly preferred is hydrogen. R3, R3a and Rsb
Preferred examples of R are, for example, those described in the preferred examples of R1, R1, and R″b above, and those different from the groups represented by R+, RIa, and Rub are particularly preferred.
4 and R4a can represent various groups since they do not significantly affect the insecticidal effect of the target product [1], for example, Cl-4 alkyl such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, etc. group, hydroxy-C+-4 alkyl group such as hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, halogeno-CI- such as bromomethyl, chloroethyl, trifluoroethyl, etc.
, alkyl group, 03-6 cycloalkyl group such as cyclopropyl, cyclopentyl, cyclohexyl, formula -(CH
A group represented by y)n R5a (symbols in the formula have the same meanings as above), etc. may be frequently used.

As R8, for example, a carbon number 1 such as methyl, ethyl, n-propyl, inpropyl, n-butyl, t-butyl, etc.
-4 lower alkyl groups are used.

n represents O or 1.

Examples of the electron-withdrawing group represented by etc.), heterocyclic oxycarbonyl (the above-mentioned heterocyclic groups are used, for example, pyridyloxycarbonyl, thienyloxycarbonyl, etc.), CI which may be substituted with halogen (C12, B etc.), etc. −
4-alkylsulfonyl (e.g. methylsulfonyl, trifluoromethylsulfonyl, ethylsulfonyl, etc.),
C5- optionally substituted with aminosulfonyl, di-C1-4 alkoxy/phosphoryl (e.g. jetoxyphosphoryl, etc.), e.g. halogen (Ci2SBr etc.), etc.
4-acyl (eg, acetyl, trichloroacetyl, trifluoroacetyl, etc.), carbamoyl, CI-4alkylsulfonylthiocarbamoyl (eg, methylsulfonylthiocarbamoyl, etc.), and the like are used. Preferred electron-withdrawing groups include, for example, nitro.

Examples of the halogen represented by Y include chlorine, bromine,
Iodine, fluorine, etc. are used, and halogens (CQ, Br
, F, etc.) may be substituted with 1 to 3 halogens such as methanesulfonyloxy, ethanesulfonyloxy, butanesulfonyloxy, trifluoromethanesulfonyloxy, etc.
Alkylsulfonyloxy having a carbon number of I to 4, which may be substituted with halogen, is used, and examples of the arylsulfonyloxy group which may be substituted with halogen include benzenesulfonyloxy, p-toluenesulfonyloxy/, p- May be substituted with 1 to 4 halokenes (C (7% Br, F, etc.) such as bromobenzenesulfonyluoquine and mesitylenesulfonyloxy?'A Elementary IA 6
-10 arylsulfonyloxy7 groups, etc. are used, and as the aceloxy group which may be substituted with halogen, for example, acetyloxy/, propionyloxy, benzoyloxy, etc. are used.

Preferred examples of the tetrahydropyrimidine compound [I] or a salt thereof include [wherein RIc and R3c) 1 Tuba formula -CR2-R''
(In the formula, Rsb represents a halogenopyridyl group or a halogenopyridyl group), where R4b represents a C1-4 alkyl group, and R4b is substituted with a C1-4 alkyl group, halogen, or C3-4 alkyl group. Indicates a C7-1° aralkyl group which may be substituted. ] There are compounds represented by the following. Here, the C3-4 alkyl group represented by R10, R3c and R4b or the C3-4 alkyl group represented by R-b
C7-10 optionally substituted with 1-4 alkyl group and -C
Aralkyl group 01-.

As the alkyl group, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, etc. are used. Chlorine, bromine, etc. are used as the halogen of the C7-10 aralkyl group, which may be substituted with chlorine, represented by R'b.

Specific examples of the C7-10 aralkyl group optionally substituted with halogen or C8- or alkyl group represented by R4b include benzyl, p-chlorobenzyl, p-methylbenzyl, phenylethyl, and the like. R5b
is, for example, 6-chloro-3pyridyl, 6-bromo-3
-pyridyl, 6-chloro-2-pyridyl, 5-bromo-
a halogenopyridyl group such as 3-pyridyl, or 2-chloro-5-thiazolyl, 2-bromo-5-thiazolyl, 2
-Represents a halogenothiazolyl group such as chloro-4-thiazolyl.

In addition, tetrahydropyrimidine compounds [+], [[a]
, [■b] salts include inorganic acids such as sulfuric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, sulfuric acid, perchloric acid, etc., such as formic acid, acetic acid, tartaric acid, malic acid, citric acid, Sychoic acid, succinic acid, benzoic acid.

Salts with organic acids such as picric acid and p-toluenesulfonic acid may also be used.

When using the tetrahydropyrimidine compound [+] or a salt thereof as an insecticide, it is necessary to use the form that general agricultural chemicals can take, that is, compound [1] or one or two of its salts.
Depending on the purpose of use, the species or species are dissolved or dispersed in a suitable liquid carrier, or mixed or adsorbed with a suitable solid carrier to form an emulsion or a third agent.

It is used in dosage forms such as wettable powders, powders, one tablet, mists, and ointments. If necessary, emulsifiers, suspending agents, spreading agents, penetrating agents, wetting agents, desiccating agents, stabilizers, etc. may be added to these preparations, and they can be prepared by methods known per se. .

The content of active ingredients in insecticides varies depending on the purpose of use; for emulsions, wettable powders, etc., it is appropriate to range from 10 to 90% by weight, and for oils, powders, etc., it is approximately 0.1 to 10% by weight. The appropriate concentration is about 1 to 20% by weight for granules, but these concentrations may be changed as appropriate depending on the purpose of use. Emulsions, wettable powders, etc., are suitably diluted and increased in volume (for example, 100 to 100,000 times) with water before use, and then sprayed.

Liquid carriers (solvents) to be used include, for example, water, alcohols (Tatoeha, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, ethylene glycol), ketones (such as acetone, methyl ethyl ketone, etc.), and ether. (e.g., dioxane tetrahydrofuran, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc.), aliphatic hydrocarbons (e.g., kerosene, kerosene, fuel oil, machine oil, etc.), aromatic hydrocarbons (e.g. , benzene, toluene, xylene.

Solvent naphtha, methylnaphthalene, etc.), halogenated hydrocarbons (e.g., methylene chloride, chloroform, carbon tetrachloride, etc.), acid amides (e.g., dimethylformamide, dimethylacetamide, etc.), esters (e.g., ethyl acetate, acetic acid, etc.) butyl, fatty acid glycerol esters, etc.), nitriles (e.g., acetonitrile).

Propionitrile, etc.) are suitable, and these solvents can be used alone or in a mixture of two or more in an appropriate ratio.

Solid carriers (diluents and bulking agents) include vegetable powders (e.g., soybean flour, tobacco flour, wheat flour, wood flour, etc.), clays such as acid clay, talcs such as talcum powder and waxite powder, diatomaceous earth, and mica powder. silica, etc.), alumina, sulfur powder, activated carbon, etc., and these can be used alone or in combination of two or more in an appropriate ratio.

Examples of ointment bases include polyethylene glycol, pectin, polyalcohol esters of higher fatty acids such as glyceryl monostearate, cellulose derivatives such as methyl cellulose, sodium alginate, bentonite, higher alcohols such as glycerin, etc. Alcohol, petrolatum, white petrolatum.

Liquid paraffin, pig intestine, various vegetable oils, lanolin.

One or more types of dehydrated lanolin, hardened lanolin, resins, etc., or a mixture thereof with various surfactants shown below may be used as appropriate.

As surfactants used as emulsifiers, spreading agents, penetrating agents, dispersants, etc., soaps, polyoxyethylene alkylaryl ethers [e.g., Neugen ■, E.N. 142 (E-A 142) ■; 9th
manufactured by Kogyo Seiyaku Co., Ltd., Nonal 0 manufactured by Toho Chemical Co., Ltd.], alkyl sulfates [eg, Emar 10. Emar 40■;
manufactured by Kao Corporation], ■ Alkyl sulfonates [e.g., inogen ■ Neogen T■
; manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neoperex 0; manufactured by Kao Corporation], polyethylene glyco-7, Ni 7-/type [Example, 7. Bohr, 8. ■, 7 Yupo 7°100, No Ball 160 ■; Sanyo Chemical Co., Ltd. 1! ], polyhydric alcohol esters [eg, Tween 200 and Tween 80; manufactured by Kao Corporation], and nonionic and anionic surfactants are appropriately used.

Additionally, the tetrahydropyrimidine compound [1] or a salt thereof and other types of insecticides (pyrethrin insecticides, organophosphorus insecticides, carbamate insecticides, etc.).

natural insecticides, etc.), acaricides, nematicides, herbicides, plant hormones, plant growth regulators, fungicides (e.g. copper fungicides, organochlorine fungicides, organic sulfur fungicides, phenolic fungicides) fungicide, etc.), synergist, attractant, repellent, pigment,
It is also possible to mix and use fertilizers and the like as appropriate.

Tetrahydropyrimidine compounds [1] and their salts are effective in controlling sanitary pests and parasitic insects on animals and plants, and show strong insecticidal effects when brought into direct contact with insects, such as by spraying directly on animals and plants infested with pests. A more distinctive property is that once the insecticide is absorbed into the plant through its roots, leaves, stems, etc., it exhibits a strong insecticidal effect when pests absorb sweat, chew on the plant, or even come into contact with it. These properties are advantageous for exterminating sweat-absorbing and biting insects.Compound [+] and its salts also have low phytotoxicity to plants and low toxicity to fish, making them suitable for use as agricultural pests. It has both safe and advantageous properties as a pest control agent.

Specifically, preparations containing the tetrahydropyrimidine compound [1] or a salt thereof are, for example,
dema rugosum), rice black stink bug (S
cotinophara 1urida), Riptortus clavatus
, Stephanitis nash
i), Laodelphax 5t
riatellus), brown planthopper (Nilapa)
rvata lugens)
Nephotettix cincticeps),
Unaspis yanone
nsis), soybean aphid (Aphis gly
cines), Japanese radish aphid (Lipaph
is erysimi), radish aphid (Br
evicoryne brassicae), cotton aphids (Aphis gossypii), hemiptera pests such as Spodoptera
a l1tura), diamondback moth (Plutella
xylostella), cabbage butterfly (Pieri)
s rapae crucivora), Chilo 5uppressalis, Autographa nigrisi
gna), tobacco moth (llel 1coverpaas)
sulta), fall armyworm (Pseudaletia)
5eparata), armyworm (Mamestra)
brassicae), Apple Brassicae (Ad)
oxophyes orana "asciata",
Cottontail moth (NoLarcha derogaLa)
), Cnaphalocrocis
Medinalis), Potatoes (Phthori)
Lepidopteran pests, such as E. maea operculella, e.g.
chnavigintioctopunctata),
Aulacophorafemorali
s), Phyllotrctast
riotata), rice black stink bug (Oulema
oryzae), rice weevil (Echinocne
Coleopteran pests such as Musca domestica, Culex pipiens pall
ens), Tabanus trigon
us), onion fly (Deliaant 1qua)
, Diptera pests such as Delia platura, Locustami locusts, etc.
gratoria), mole (Gryllotalpa)
africana), such as the German cockroach (BlatLella germanic).
a), Periplaneta I'
Cockroach pests such as Tetranychus uliginosa, Tetranychus urticae
), orange spider mite (Panonychus citr
i), Tetranychus k
Anzawai), Tetranyc
Pests of the order Acari such as the apple spider mite (Panonychus ulmi), the apple spider mite (Panonychus ulmi), and the orange rust mite (Aculops pelekassi), such as the rice nematode (^phelen)
It is particularly effective in controlling nematodes such as choides besseyi).

The insecticide of the present invention thus obtained is safe and has extremely low toxicity, and is an excellent agricultural chemical. The insecticide of the present invention can be used in the same manner as conventional insecticides, and as a result, it can exhibit superior effects compared to conventional products. For example, the insecticide of the present invention can be used against target pests by, for example, spraying foliage on a crop treated with a nursery box, spraying insect bodies, or using water [
It can be used by water application or soil treatment. The application amount can vary widely depending on the application time, application location, application method, etc., but generally the active ingredient (tetrahydropyrimidine compound [11 or its salt)] is 0.3 g per hectare. ~30
It is desirable to apply it in an amount of 0.00 g, preferably 50 g - 1.00 g. In addition, when the insecticide of the present invention is a hydrating agent, the final concentration of the active ingredient is 0.1 to 1000.
It may be used after being diluted so as to have a ppm preferably in the range of 10 to 500 ppm.

The tetrahydropyrimidine compound [1a] or a salt thereof can be produced by the following methods (A) to (F). When the compound [ral is obtained in the form of a free compound, it can be converted into a salt as described above, and when it is obtained in the form of a salt, it can be converted into a free compound according to a conventional method. In addition, compound [1a]
When the compound contained in the compound [ral , [11], [[], [IV], [V], [■
], including its salts (for example, salts with acids such as those described in compound [1] above), simply compound [1a]
, [11], [111], [lV], [V], [VI]
It is abbreviated as.

(A) Compound [ral] is left by reacting compound [11], compound [111], and formaldehyde.

Compound [II] and compound [I11] may be used in their free form, but they may also be used as appropriate in the form of a salt as described for compound [1] above. For compound [n], compound [[
[ ] is about 1.0 to 1.5 equivalents, formaldehyde is about 2 equivalents
It is preferable to use ~4 equivalents, but if there is no problem with the reaction, about 1.5 to 10 equivalents of compound [In] and about 4 to 20 equivalents of bomaldehyde may be used.

The form of formaldehyde used in this reaction is usually an aqueous solution (formalin), but it may also be paraformaldehyde or gaseous formaldehyde.

Although the reaction may be carried out without a solvent, it is usually carried out in a suitable solvent. Such solvents include, for example, water, alcohols such as methanol, ethanol, n-propatool, impropatool, etc., aromatic hydrocarbons such as benzene, toluene, xylene, etc., halogenated hydrocarbons such as dichloromethane chloroform, etc. For example, saturated hydrocarbons such as hexane, heptane, chloride, etc., ethers such as diethyl ether, tetrahydrofuran (hereinafter abbreviated as THF), dioxane, ketones such as acetone, nitrites such as acetonitrile, etc. , for example, sulfoxides such as dimethyl sulfoxide (hereinafter abbreviated as DMSO), such as N,N dimethylformamide (hereinafter abbreviated as DMSO), etc.
It is abbreviated as MF.

), esters such as ethyl acetate, and carboxylic acids such as acetic acid and propionic acid. These solvents can be used alone, or two or more of them can be used as a mixture in an appropriate ratio, for example, from 1:1 to 1:IO, if necessary. If the reaction mixture is not a homogeneous phase, phase transfer catalysts such as quaternary ammonium salts such as triethylpencylammonium chloride, tri-n-octylmethylammonium chloride, trimethyldesylammonium chloride, and tetramethylammonium bromide, or crown ethers may be used. The reaction may be carried out in the presence of

This reaction may advantageously proceed in the presence of an acidic substance. As such acidic substances, for example, hydrohalic acids such as hydrochloric acid and hydrobromic acid, lower carboxylic acids such as phosphoric acid, acetic acid, and propionic acid are used in a catalytic amount to a large excess.

This reaction usually proceeds at 0 to 40'C, but may be heated as appropriate (40'C).
0 to 100°C) to shorten the reaction time.

The reaction time is usually 2 to 20 hours without heating.
When heated, the time is about 10 minutes to 5 hours.

(B) Compound [1a] is produced by reacting compound [IV] and compound [V].

Compound [IV] and compound [V] may be used in their free form, but they may also be used appropriately as a salt as described for compound [1] above. It is preferable to use about 0.8 to 1.5 equivalents of compound [■] relative to compound [IV], but it may be used in an amount of about 1.5 to 10 equivalents if there is no problem with the reaction.

This reaction is carried out without a solvent or in a solvent such as those mentioned in method (A). If the reaction mixture is not homogeneous, a phase transfer catalyst as described in method (A) may be used.

This reaction may be promoted by a base or a metal salt. Such bases include, for example, sodium bicarbonate, potassium bicarbonate, and sodium carbonate.

Potassium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, phenyllithium, butyllithium,
Sodium hydride, potassium hydride.

Sodium methoxide, sodium methoxide.

Inorganic bases such as metallic sodium and metallic potassium, such as triethylamine, tributylamine, N.

N-methylaniline, pyridine, lutidine colicin, 4-(dimethylamino/)pyridine, DI3U(l,8
An organic base such as -diazabicyclo[5,4,01undecene7) can be used. The organic base itself can also be used as a solvent.

Metal salts such as copper chloride, copper bromide, copper acetate,
Copper salts such as copper sulfate, mercury salts such as mercury chloride, mercury nitrate, and mercury acetate can be used.

The reaction temperature of this reaction is -20°C - 150°C, the reaction time is 10 minutes to 20 minutes, but preferably each O0
C~80'CS 1 hour~1O hour.

Furthermore, the tetrahydropyrimidine compound [I''] can also be produced by reacting the compound [VI] or a salt thereof with the compound [■].The following (C) to (F
).

(C) When using the compound [VI] with R2a=II or a salt thereof as a raw material, that is, the compound represented by the formula ([wherein, Rla, R3aSR4 and X have the same meanings as above. By reacting with 1, the compound [1al can be produced.

Compound [■1 is about 0.8-1
．． It is preferable to use 5 equivalents, but a large excess amount may be used if there is no problem with the reaction.

This reaction may be carried out in the presence of a base to promote the reaction, and as such a base, those described in Method (+3) can be used. The base is the compound [VI
0.5 equivalent to a large excess of rats, approximately 0.
8 to 1.5 equivalents can be used. Moreover, when using an organic base, it can also be used as a solvent itself.

This reaction is usually preferably carried out in a solvent as described in Method PI (A), and if a homogeneous reaction system is not desired, a phase transfer catalyst as described in Method (A) may be used. .

The reaction temperature is usually -20 to 150'C1, preferably O to
It is 80'C. The reaction time is usually 10 minutes to 50 hours, preferably 2 hours to 20 hours.

(■)) When using a compound [■] with R4a=H or a salt thereof as a raw material, that is, by reacting a compound represented by the formula "Symbols in the formula have the same meanings as above" and the compound [■] Compound [+a] can be produced. This reaction can be carried out according to the same conditions as described in method (C).

(E) When using a compound [Vl] with R3a=H or a salt thereof as a raw material, that is, by reacting a compound represented by the formula [symbols in the formula have the same meanings as above] with a compound [■] [1a] can be produced. This reaction can be carried out under the same conditions as described in method (C).

(F) IjW14ToLteR3a=R'-H conversion at
When using l[VI]ma or a salt thereof, in other words, compound [Ia] is produced by reacting a compound represented by the formula (the symbols in the formula have the same meanings as above) and compound [■] be able to. This reaction can be carried out according to the same conditions as described in method (C), but in this case, compound [■] is about 1.5 to 2
．． It is preferable to use 5 equivalents, and when a base is used to promote the reaction, it is preferable to carry out the reaction in the presence of about 1.5 to 3 equivalents of base.

The compound [L a] or a salt thereof thus obtained can be prepared by known means, such as I-layer line, vacuum concentration, and distillation.

It can be isolated and purified by fractional distillation, solvent extraction, liquid conversion, dissolution, chromatography, crystallization, recrystallization, etc.

The base vehicle of the above-mentioned method of the present invention [the compound used as the substance]
11] can be manufactured, for example, by the method according to [Figure 1] and [Figure 2].

[figure 1] [figure 2] [V] [All symbols in the formula have the same meanings as above.

] [Figure 1] Method 2 (Step 1) Compound [V] and Compound [■] are mixed without solvent or in a solvent such as that described in Method (A) (for example, ether, THF, dichloromethane, chloroform, acetone,
Aprotic solvents such as acetonitrile and toluene are preferred. ) to obtain compound [IK]. This reaction can also be promoted by adding a base as described in method (B). Reaction temperature.

The reaction time varies greatly depending on R+a and RtBa, but is preferably O'C-130°C, 40 minutes to 10 hours. Compound [■] is usually 0.
8 to 1.5 equivalents are used.

(Step 2) Compound [IX] is reacted with a methylating agent such as methyl iodide, methyl bromide, dimethyl sulfate, etc. to obtain compound [X]. This reaction is preferably carried out in a solvent as described in method (A), and a base as described in method (B) may be added to accelerate the reaction. Normal reaction temperature is 0°C-100°C1 reaction time is 30 minutes to 10 minutes.
within the time range. The methylating agent is usually used in an amount of 1.0 to 2.0 equivalents relative to compound [IX].

(Step 3) Compound [X] and compound [XII are reacted,
Compound [11] is obtained. This reaction can be carried out under the conditions described in method (B), but the reaction temperature is 80'C to 1
50'c, the reaction time may be from 5 hours to 100 hours, and the reaction may be carried out using a solvent amount of compound [XII.

Method of [Figure 2]: (Step 1) Compound [V] was added to 0.0% of compound [XII].
8 to 1.5 equivalents are used. Usually at 60℃~100℃, 1
It is preferable to react for 10 hours to 10 hours. Compound [XII[] is obtained by otherwise following the conditions described in method (B).

(Step 2) For compound [X[[], compound [XIV]
0.8 to 5 equivalents of are reacted to obtain compound [11]. The reaction conditions for the reaction mixture may be as described in step 1).

(Step 1'), (Step 2') respectively (Step 1), (
Compound [XV] and compound [11] are obtained according to the reaction conditions described in step 2).

The compound and raw material compound [II] obtained in each step of [Figure-1] and [Figure-2] can be used as the next step [Production source 4) after being separated by the above-mentioned known means, for example. Alternatively, the reaction mixture can be used as a raw material in the next step as long as it does not interfere with the reaction in the next step.

Among the raw materials used in the methods shown in Figure 1-11 and Figure 1-2 above, compound [V] is used, for example, in the "New Experimental Chemistry Course" (
It can be synthesized by the method described in ``New Experimental Chemistry Course'' (Marukubi), vol. 14-1111, pages 1332-1399, etc., or by a similar method such as C removal, etc., and the compound [■] can be synthesized, for example, by the method described in "New Experimental Chemistry Course" (Marukubi), +4- +1I volume, 1503-15
It can be synthesized by the method described on page 09 or a similar method. In addition, compound [XIl]
For example, Chem.

Ber, ), I O0, page 591 (+967), etc., or a method similar thereto, etc. Compound [XIV] can be synthesized, for example, by a method similar to that of compound [VJ. .

In addition, in the raw materials for the method of the present invention, compound [■] can be synthesized, for example, by the same method as that for compound [V] already described, and some of compounds [, IV] are known compounds, such as " It can be produced by the method described in "Yakugaku 21L Magazine", Volume 97, Page 262 (1977) or a method similar thereto, and the compound [■ is for example "New Experimental Chemistry Course" (round neck) 14- Volume 1, 307~
450 pages, same volume It-11.

Pages 1120-1133, volume 14-■ 11793-
It can be synthesized by the method described on page 1798 or a similar method.

In addition, compound [VI] and its specific example compound [Vla
], [VIb], [■c], [■d] High-remo compound [Ia] Since it is a compound included in [Ia], it should be manufactured according to the manufacturing method (A) or (B) of the already mentioned compound [1''1. Can be done.

Effects Tetrahydropyrimidine compound [I] and its salts have excellent insecticidal activity, and this is clear from the following test examples.

Test Example 1 Brown planthopper (Nilaparvata)
5 mg of the test compound (indicated by the compound number obtained in the example below) was added to the stems and leaves of two-leaf stage rice seedlings grown in a seedling box.
Rai-7□□. 8□) 0.5m containing 20cm (7) Dissolve in acetone and dilute 3000 times with Dyne (spreading agent, manufactured by Narita Pharmaceutical Co., Ltd.) water to a specified concentration (500 ppm) C
! : Then, 10 d/paperbot of 1 liquid was sprayed with a spray gun. After pouring water into the bottom of a test tube and placing the treated rice seedlings there, 10 3rd instar brown planthopper larvae were released and the tube was capped with an aluminum stopper. This test tube was placed in a constant temperature room at 25°C.
Dead insects were counted 7 days after release. The mortality rate was calculated using the following formula, and the results are shown in Table I.

Table-1 Mortality rate (%) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 00 00 00 00 00 00 100 00 00 00 00 00 00 00 00 00 00 00 0 0 0 0 0 0 0 0 0 0 0 This table = 1 reveals that tetrahydropyrimidine [1] or its salt has excellent insecticidal activity against brown planthoppers.

Test Example 2 Spodoptera 1
effect on soybean seedlings (single leaf development stage).Nmg of the test compound (indicated by No. of the compound obtained in the following example) was dissolved in 0.5Ml of acetone containing Tween 20.
A predetermined IN a (500 ppm) was applied with twice diluted dyne water, and 20 d/pot of the chemical solution was sprayed using a spray gun. After the chemical solution has dried, two middle leaves of the soybean are cut out, placed in an ice cream cup, and the 3rd instar larval IO head of Spodoptera japonica is released.After the adult, the cup is placed indoors (25°C), and the dead forms are counted after 2 days. Ta. The mortality rate was calculated using the formula shown in Test Example 1, and the results are shown in Table 2.

Table-2 Compound no.

0 3 4 5 7 4 8 1 3 4 5 6 7 2 3 4 5 3 6 7 8 9 Mortality rate (%) 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 OO OO This Table-2 proves that tetrahydropyrimidine [1] or its salts have excellent insecticidal activity against Spodoptera spp.

Next, the present invention will be explained in more detail with reference to Examples and Reference Examples, but the present invention should not be limited to these Examples.

The elution in column chromatography of Examples and Reference Examples was performed using TLC (Th1n LayerChrom).
The analysis was carried out under observation using atography+ (thin layer chromatography). In TLC observation, TLC
The plate was Kieselgel 60 F t5. manufactured by Merck. (70 to 230 meshes), the solvent used as the elution solvent in column chromatography was used as the developing solvent, and a UV detector was used as the detection method. As the silica gel for the column, Kieselgel 60 (70 to 230 mesh), also manufactured by Merck, was used. NMR
Spectra show proton NMR, VARIAN EM39 using tetramethylsilane as internal reference.
The total δ value was determined in ppm using a 0 (90 MHz) type spectrometer. When using a mixed solvent as a developing solvent, the values shown in parentheses are the contents of each solvent! 1 is the mixing ratio.

In addition, the abbreviations used in the following Examples, Reference Examples, and Table 3 have the following meanings.

Me: methyl group, Et: ethyl group, n-Pr: n-propyl15. 1-Pr: isopropyl group, t-Bu
: t-methyl group, Ph: phenyl group, s: single l', br broad (broad), d: doublet,
t nitribulet, q: quartet 1m: multibullet, dd doublet doublet, J: coupling constant fiz Hertz, CDC1: heavy chloroform, DMSOde heavy DMSO, %: weight %, Mp:
Reference to melting point or room temperature means about 15-25°C.

Reference Example 1 87.4 g of thionyl chloride, 1,2-dichloroethane to
2-chloro-
5-(hydroxymethyl)pyridine 70°3g and 1,2
- dropwise addition of a mixture of 50 ml of dichloroethane over 30 minutes;
Thereafter, the mixture was stirred at room temperature for 1 hour and 30 minutes, then heated under reflux for 4 hours and 30 minutes. After condensing 1g3, add 20% chloroform to the residue.
0 m4 and 60 d of water were added, and while stirring, 20 g of sodium hydrogen carbonate was added little by little. Separate the organic layer;
After treatment with activated carbon, it was concentrated to yield 75.9 g of 2-chloro-5-(
chloromethyl)pyridine was obtained as a tan solid.

'II NMR(CDC(!3): 4.57(2
11, s), 7J4 (lit, d.

J-8,511z), 7.72(ill, dd,
J=8.5.2.511z), 8.40(IH,d
, J = 2.5tlz) Reference Example 2 2-chloro-5-1chloromethyl)pyridine 14°99
g, 63.01 g of 25% ammonia water, and 60 d of acetonitrile were placed in a stainless steel pressure-resistant reaction vessel.
Stir in a 41]l valley at 80°C for 2 hours. (add 30% hydroxide to the reaction mixture) l) 12.3 g of rum aqueous solution
was added and concentrated. Add 200m of ethanol to the residue,
It was dried over anhydrous magnesium sulfate, and the insoluble matter was filtered out. 2
After concentrating the solution, column chromatography (developing solvent;
Purified with dichloromethane-meth/-ol (4:1),
7.66 g of 5-(aminomethyl)-2-chloropyridine was obtained as a yellow solid.

'HNMR(CDC(!3): 1.60(2+1.
S), 3.90 (2+1.S), 7.28 (lft
, d, J= 8.51! z), 7.67(ill
, dd, J= 8.5.2゜5! Iz), 8.3
3(lit, d, J = 2.511z) Similarly, 5-(aminomethyl)-2-bromopyridine, 5-(
Aminomethyl)-2-chlorothiazole and 5-(aminomethyl)-2-(4-chlorophenoxy)pyridine were obtained.

Reference example 3 36g of 40% methylamine aqueous solution and 20g of acetonitrile
A mixed solution of 15.05 g of 2-chloro5-(chloromethyl)pyridine and 50 d of acetonitrile was added dropwise to the mixed solution of 0d at room temperature over 1 hour, and the mixture was further stirred for 1 hour and 30 minutes. The reaction mixture was concentrated, 100 d of water was added to the residue, neutralized with heavy soap, saturated with sodium chloride, extracted with dichloromethane (200 d×2), the organic layer was dried over anhydrous magnesium sulfate, concentrated, and the residue was filtered into a column. Chromatography (Developing solution 15 Nidichloromethane-methanol (4:
1)) to give 8.77 g of 2-chloro-5=(
Methylaminomethyl)pyridine was obtained as a yellow-brown body.

'If NMR (CDCf23): 1.30 (I
II, br, s), 2.44 (3H, s), 3.7
5 (2H, s), 7JO (IH, d, J = 8.411
z), 7.68 (IH, dd, J= 8.4.2
．． 4tlz), 8.35(III, d, J=2
．． 411z) Similarly, 2-chloro-5-(ethylaminomethyl)pyridine, 2-chloro-5-(isopropylaminomethyl)pyridine, 2-(4-chlorophenoxy)-5-(ethylaminomethyl)pyridine and 3-(
methylaminomethyl)pyridine was obtained.

Reference example 4 2-chloro-5-(methylaminomethyl)pyridine 2.
About 20° to a mixed solution of 81 g and 10 d of dichloromethane.
A dichloromethane 2d solution of 144 g of methyl inthiocyanate was added dropwise to the aqueous solution of C over 10 minutes. After stirring for 30 minutes, the reaction mixture was concentrated and the residue was subjected to column chromatography (developing solvent: dichloromethane-methanol (2
0+1)) to give 3.33 g of 1-(6-chloro-
3-pyridylmethyl)-1,3-dimethylthiourea?
4.

In a mixed solution of 2.56 g of the above thiourea and THF2Q,
Under water cooling, sodium hydride (al+, 60%) 0.2
94 g was added little by little and stirred for 30 minutes.

Under water cooling, 1.74 g of iodomethane was added to T F (F 21d
The solution was added dropwise over 5 minutes, and after standing at room temperature for about 3 hours, it was concentrated, 50 bulbs of dichloromethane were added, and the mixture was washed with water. After concentrating the organic layer, 200% of nitromethane was added, and the mixture was heated under reflux for 12 hours. After condensing 1g9 of the reaction mixture, column chromatography (developing solvent dichloromethane-methanol (9:
l)) to give 1.63 g of 1-[N-(6-chloro-3-pyridylmethyl)-N-methylaminoco-1
-Methylamino-2nitroethylene was obtained. Mp103
〜+04°C The following compounds were obtained in the same manner.

1-[N-(6-chloro-3-pyridylmethyl)-N-
Ethylaminoco-1-methylamino-2-nitroethylene.

1-[N-(6-chloro-3-pyridylmethyl)N-isopropylaminoco-1-methylamino 2-nitroethylene.

1-EN-(6-chloro-3-pyridyl)-N-methylamino 1-1-methylamino-2-nitroethylene.

1-[N-[6-(4-chlorophenoxy)-3-pyridylmethyl]-N-ethylamino]-1-methylamino-2-nitroethylene.

Reference example 5 1.1-bis(methylthio)-2-nitroethylene6.
4.28 g of 5-aminomethyl-2-chloropyridine was added dropwise to a mixture of 61 g of acetonitrile and 100 d of acetonitrile under heating under reflux over 3 hours and 30 minutes, and the mixture was further heated under reflux for 2 hours.

When cooled, insoluble matter (by-product 1,1-bis(6-chloro-3
-pyridylmethylamino)-2-nitroethylene) was removed by filtration, the filtrate was concentrated, and washed with ethyl acetate.
3g of 1-(6-chloro-3-pyridylmethylamino)
-1-methylthio-2-nitroethylene was obtained. The ethyl acetate wash was concentrated and the residue was subjected to column chromatography (developing solvent).

Further purification with dichloromethane-methanol (30:1) gave 1.15 g of the above compound.

The following compounds were obtained in the same manner.

1-[N-(6-chloro-3-pyridylmethyl)-N-
Methylaminoco-1-methylthio-2-nitroethylene.

1[N-(6-chloro-3-pyridylmethyl)N-ethylaminoco-1-methylthio-2-nitroethylene.

1-(N-methyl-N-pyridylmethylamino)=1-
Methylthio-2-nitroethylene.

1-(6-Bromo-3-pyridylmethylamino)l-methylthio-2-nitroethylene.

1-[6-(4-chlorophenoxy)-3-pyridylmethylaminoco-1-methylthio-2-nitroethylene.

1-(6-chloro-3-pyridylamino)-1-methylthio-2-nitroethylene.

1-Methylthio-1-(3-pidylmethylamino)-
2-nitroethylene.

1-(2-chloro-5-thiazolylmethylamino)-1
-Methylthio-2-nitroethylene.

Reference example 6 ■-(6-chloro-3-pyridylmethylami/)-t-
2.0 g of methylthio-2-nitroethylene.

40% methylamine aqueous solution 1.8g, acetonitrile 2
After heating the 0 m mixture under reflux for 3 hours, it was concentrated, and the residue was washed with dichloromethane to remove 1.73 g of 1-(6-chloro-3-pyridylmethylami/)-1-methylamino-2-nitroethylene. Obtained.

Mp181~183°C The following compounds were obtained in the same manner.

1-(6-chloro-3-pyridylmethylamino)-1-
Dimethylamino-2-ditroethylene.

1-(6-chloro-3-pyridylmethylamino)=1-
Ethylamino-2-nitroethylene.

1.1-bis(6-chloro-3-pyridylmethylamino)-2-nitroethylene.

1-amino-1-(6-chloro-3-pyridylmethylamino)-2-2!・Loethylene 1-(6-chloro-3~
Pyridylmethylamine/)1i Sobropylamino-2-nitroethylene 1-amino-1-[N-(6-chloro-3
-pyridylmethyl)-N-methylaminoco-2-2-
o Ethylene.

■-Ami7-1-[N-(6-chloro0-3-pyridylmethyl)-N-ethylaminoconitronitroethylene.

1-Amino-1-(N-methyl-N-pyridylmethylamine)-2-nitroethylene.

1-(6-bromo-3-pyridylmethylamino/)l-methylamino-2-nitroethylene 1-[6-(4-chlorophenoquine)-3-pyridylmethylamino-1-methylamino-2- Nitroethylene.

1-(6-chloro-3-pyridylamino)-1methylamino-2-nitroethylene.

1-ami7-1-(3-pyridylmethylamino)-2-
Nitroethylene 1-(2-chloro-5-thiazolylmethylamide/)-1
-Methylamino-2-nitroethylene.

Reference example 7 1-methylamino-1-methylthio-2-nitroethylene 5.93g, 37% formaldehyde water soluble i&7.1
5g, 40% in a mixture of 10M acetonitrile under water cooling.
Methylamine aqueous solution 3.42g acetonitrile 10d
The solution was stirred at room temperature for 8 hours at IDff for 30 minutes and then for 0 minutes. - After leaving the room 1. Agricultural reduction and column chromatography (developing solvent dichloromethane-methanol (20:
1)), 582 g of 1,3-dimethyl-4
-Methylthio-5nitro-1,2,3,6-titrahyF
I got a Robiri sewing machine. syrupy liquid.

INMR(CDC(!3): 2.43(31
1,s), 2.50(3!I,s).

3, 29 (311, s), 3.77 (211, s),
3.86 (211, s).

Similarly, the following compounds were obtained.

1-ethyl-3-methyl-4-methylthio-5nitro-
1,2,3,6-titrahydrobyrimidi-3-methyl-4
-methylthio-5-nitro-l-propyl-1,2,3
, 6-titrahydrobyrimidine.

l-isopropyl-3-methyl-4-methylthio-5-
Nitro-1,2,3,6-titrahydropyrimidine.

3-Methyl-4-methylthio-5-nitro-1-phenyl-1,2,3,6-titrahydropyrimidine.

3-ethyl-1-methyl-4-methylthio-5nitro-
1,2,3,6-titrahydropyrimidine.

3-(6-chloro-3-pyridylmethyl)-1=methyl-4-methylthio-5-nitro-1,2,3°6-titrahydropyrimidine.

3-(6-chloro-3-pyridylmethyl)-1ethyl-
4-Methylthio-5-nitro-1,2,36-titrahydropyrimidine.

4-Methylthio-5-nitro-13-bis(3-pyridylmethyl)-1,2,3,6-titrahydropyrimidine.

Example 1 Al 1 1-[N-(6-chloro-3-pyridylmethyl)N-methylaminoco-1-methylamino-2-nitronythylene 0.898 g, 40% methylamine aqueous solution 0.31 g,
Ethanol 57. Add 37% to a mixture of 5 gallons of THF under water cooling.
0.601 g of formaldehyde aqueous solution was added dropwise over 20 minutes, and the mixture was stirred at room temperature overnight. After concentration, column chromatography (developing solvent: dichloromethane-methanol (1
0:l)) and 1. oog 4-[N-(6-chloro-3pyridylmethyl)-N-methylami/]-1,
3dimethyl-5-nitro-1,2,3,6-titrahydrobyrimidine (Compound No. I) was obtained. syrupy liquid.

Elemental analysis (CI3H18N 50, CQ) calculated value C
: 50.08, H: 5.82, N: 22.46 Actual value C: 49.94, H: 5.60, N: 2
2.62'HNMR (CDCf2a): 2.44 (
311, s), 2.80 (311, s).

3.08 (311,s), 3.60 (211,s),
3.69 (21 (, s), 4.1~46 (21, m
), 7.36 (lit, d, J=8.511z),
7.73 (III, dd.

J=8.5.2.511z), 8.34(III,
d, J = 2.511z).

Example 2 l-(6-chloro-3-pyridylmethylamino)1-methylami/-2-nitroethylene 0.52 g, t-
To a mixture of 0.20 g of butylamine and 5M acetonitrile, 0.50 g of a 37% formalin aqueous solution was added dropwise over 10 minutes under water cooling, and the mixture was stirred for 1 hour under water cooling and for 2 hours and 30 minutes at room temperature. The reaction mixture was concentrated, and the residue was purified by column chromatography (developing solvent, ethyl acetate). First, 0.52 g of 1L-butyl-4-(6-chloro-3-pyridylmethylamino)-3-methyl- 5-nitro-1,
2゜3.6-titrahydrobyrimidine (compound No. I
7) and 1-1-butyl-3-(6-chloro-3-pyridylmethyl)-4-methylamino-5-nitro-1°2.
A mixture of 3.6-titrahydropyrimidine (compound N044) was obtained. From this mixture, compound No. 44 and compound No. 4 were determined by more precise column chromatography.
, 17 (distilled in this order) were separated.

Compound No. 17: Mp 169-170°C1 (
NMR(δ, CD C123): 1.13
(9tl, s), 2.97 (311°s), 3
．． 63 (211,s), 3.72 (211,s),
4.53 (2tl, d, J = 6°011z)
, 7.35 (III, d, J=8.511z), 7
．． 73 (211, dd, J=8°5.2.511z),
8.37 (lit, d, J=8.511z), 10
．． 43 (IH, br.

t, J = 611z) Compound No. 44: Mp 160-161°C'H
NMR (δ, CD CR3): 1.04 (9H
, s), 3.03 (3H.

d, J = 611z), 3.55 (211,s)
, 3.72 (211,s), 4.36 (211゜s
), 7.40 (IH, d, J-8, 5tlz), 7
．． 75 (Ill, dd, J=8.511z, 2.511
z), 8.45 (lit, d, J=2.5tlz),
10.42 (ill.

br, s) Example 3 1.3-dimethyl-4-methylthio-5-nitro-12
, 3,6-titrahydropyrimidine 0.61g 13-pyridylmethylamine 0.357g, acetonitrile 6d
After stirring the mixture at room temperature for 5 hours, it was concentrated and purified by column chromatography (developing solvent: dichloromethane-methanol (10:l)) to obtain 0.33 g of 1.3-
Dimethyl-4-(3pyridylmethylamino)-5-nitro-1,2°3.6-titrahydropyrimidine (Compound No. 31) was obtained. syrupy liquid.

Elemental analysis value (C, Hl?N 50 z) Calculated value C:
54.74, H: 6.51. N: 26.60
Actual value C: 54.62, H: 6.36, N:
26.41HNMR (CDCf2a): 2.39 (3
tl, s), 3.12 (311, s).

3, 67 (2H, s), 3.78 (2H, s), 4
．． 59 (211, d, J= 5.711z), 7.2
~7.45 (IH, m), 7.65 ~ 7.85 (IH
, m), 8.5-8, 7 (211, m), 10.8
6 (III, br, t, J = 5.711z)
Example 4 4-(6-chloro-3-pyridylmethylamino) 1.3
-dimethyl-5-nitro-1,2,3,6 tetrahydropyrimidine (compound No. 13) 0.27 g, dry TH
To a mixture of F5d and dry acetonitrile 5d, under water cooling,
0.0239 g of sodium hydride (60%, oily) was added portionwise over 1 minute.

After stirring at room temperature for 30 minutes, under water cooling, formic acid acetic anhydride 0
．． 24 g of THFld solution was added dropwise over 4 minutes, and
I stirred for hours. After concentration, column chromatography (developing solvent, dichloromethane-methanol (20:1)
)) to give 0.14 g of 4-[N(6-chloro-
3-pyridylmethyl)-N-formylamino]-1,3
-dimethyl-5-nitro-1°2.3.6-titrahydropyrimidine (compound no.

30) was obtained as a syrupy liquid.

'HNMR(δ, CD CQ3>: 2.41(
311, s), 2.93 (38°s), 3.6~4
．． 0 (4tl, m), 4.63 (IH, d, J=14
．． 711z).

4, 87 (IH, d, J= 14.7Hz), 7.
33 (lit, d, J=8.511z).

7, 78 (IH, dd, J= 8.5.2.511z
), 8.21 (lit, s), 8.32 (IH,
d, J = 2.5Hz) Compounds shown in Table 3 below were manufactured according to the above-mentioned manufacturing method of the present invention or Examples 1 to 4. Table 3 also includes the compounds obtained in Examples 1 to 4.

Gun ’+1 Saho-ni Phrases,.

=i engineering Chuf minister *8 people Ku　　　Φ and bell One tremor 40.

Table 4 Continued Example 5 Compound No. 2 (20% by weight), xylene (75', f
[jff1%) and polyoxyethylene glycol ether (Nonipol 85■) (5% by weight) were mixed well.
An emulsion was produced.

Example 6 Compound No. 7 (30% by weight), sodium ligninsulfonate (5% by weight), polyoxyethylene glycol ether (Nonipol 85■) (5?Ifffi%).

White carbon (30% by weight), clay (30% by weight)
) were mixed well to produce a water mouthwash.

Example 7 Compound No. 13 (3% by weight), white carbon (3% by weight)
% by weight) and clay (94% by weight) and mix well to make a powder! I left 2.

Example 8 Compound No. 17 (10% by weight), sodium ligninsulfonate (5% by weight), and clay (85% by weight) were thoroughly ground and mixed, water was added, and the mixture was thoroughly kneaded, then granulated and dried to form granules. The drug was manufactured.

Effects of the Invention The present invention contributes to agriculture by providing an excellent insecticide.

Claims (5)

[Claims] (1) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1, R^2, R^3 and R^4 are the same or different, hydrogen, an optionally substituted hydrocarbon group, or X represents an optionally substituted heterocyclic group and an electron-withdrawing group. ] An insecticide characterized by containing a tetrahydropyrimidine compound or a salt thereof. (2) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1^a, R^2, R^3^a and R^4 are the same or different and may be hydrogen or substituted. A hydrocarbon group or an optionally substituted heterocyclic group, R
At least one of ^1^a and R^3^a has the formula -(CH
_2) _n-R^5 (wherein R^5 represents an optionally substituted heterocyclic group or substituted hydrocarbon group, n represents 0 or 1), and X represents an electron-withdrawing group. Indicates the group. ] A tetrahydropyrimidine compound or a salt thereof. (3) The tetrahydropyrimidine compound or a salt thereof according to claim (2), wherein R^5 is halogenopyridyl or halogenothiazolyl. (4) Claim (1) wherein the tetrahydropyrimidine compound or its salt is the compound according to claim (2) or (3).
) listed insecticides. (5) (i) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1^a, R^2, R^3^a and X indicate the same meaning as described in claim (2) . ] or a salt thereof and the formula R^4-NH_2 [wherein R^4 has the same meaning as described in claim (2). ]
By reacting formaldehyde with amines represented by amines or their salts, or (ii) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^3^a, R^4 and ), R^6 represents a lower alkyl group. ] or its salt and the formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R^1^a and R^2 have the same meaning as described in claim (2). ], or (iii) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1^b, R^2^a, R^3^ b and R^
4^'a represents at least one hydrogen and the other represents an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group, and X has the same meaning as described in claim (2). ] or a salt thereof and the formula R^7-Y [wherein R^7 is an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group, and Y is a halogen or a halogen represents an alkylsulfonyloxy group, an arylsulfonyloxy group, or an acyloxy group which may be substituted with . ] There are formulas ▲ mathematical formulas, chemical formulas, tables, etc. that are characterized by reacting with compounds represented by [where R^1^a, R^2, R^3^a, R^4 and X indicates the same meaning as described in claim (2). ] A method for producing a tetrahydropyrimidine compound or a salt thereof.