JPS6025994A - 5-methylthiopyrimidine, its preparation, and insecticide - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (R<1> is lower alkyl, alkenyl, alkynyl, phenyl, or benzyl; R<2> is lower alkyl; X is O, or S). EXAMPLE:2,4-Dimethoxy-4-methylthio-6-(O,O-diethylphosphoryloxy)pyrimid ine. USE:An insecticide. PREPARATION:A 2,4,6-trialkoxypyrimidine is hydrolyzed with a mineral acid to give a 5-methylthio-6-hydroxypyrimidine (e.g., 2,4-dimethoxy-5-methylthio-6-hydroxypyrimidine, etc.). This compound and a base such as potassium carbonate, etc. are dissolved or dispersed into a solvent such as dimethylsulfoxide, etc. A halide (e.g., diethyl chlorophosphate, etc.) shown by the formula III (Hal is halogen) is gradually dropped to the solution or dispersion, and they are reacted preferably at 0 deg.C- room temperature for 1- several hours.

Description

Detailed Description of the Invention: (In the formula, R1 is a lower alkyl group, an alkenyl group, an alkynyl group, a phenyl group, or a benzyl group, R, is a lower alkyl group, and X is an oxygen atom or a first-class yellow atom. The present invention relates to 5-methylthiopyrimidines represented by (1), a method for producing the same, and an insecticide characterized by containing the compound as an effective component (1).

A great deal of research has been carried out on pyrimidine derivatives, and a huge number of mosquito compounds have been synthesized, and many compounds that exhibit distinctive live-beating activity have been discovered in the field of agricultural medicine. . However, most of them are easily produced by modifying substituents at the 4- and 6-positions of the pyrimidine skeleton.

The 5-position has low reactivity, and only a few methods are known in which nitration, halogenation, etc. are carried out under limited conditions in order to directly introduce a substituent.

Among the substituents at the 5-position, there are few examples of synthesis of pyrimicines that sometimes have a methylthio group.

The present inventors have a methylthio group at the 5-position, and
+4 Focusing on the fact that no compounds having an alkoxy group at the 4y-position and a phosphoryloxy group at the 6-position have ever been synthesized, we synthesized various pyrimidines and investigated their physiological activity. As a result of testing, it was found that the compound of the present invention has an extremely superior control effect on various insect pests, mites, and nematodes, compared to existing chemicals, and the present invention was completed.

Compound 1 represented by the general formula (I) of the present invention is used in the order Hemiptera, Phylphoptera, Coleoptera, Diptera, Orthoptera, Orthoptera, etc. (,
It has an excellent insecticidal or control effect against insects, mites parasitic on plants and animals, and stubborn nematodes. It can be effectively used as a control agent for the extermination and control of second pests and animal parasites in the field of veterinary medicine.

The compound of the present invention is represented by the general formula (IT,) Cl-13 (wherein R' has the same meaning as above);
．． z+-dialkoxy 6-hydroxypyrimidines are represented by the general formula (ill) (wherein, Hal represents a loken atom, It and X
has the same meaning as above) in the presence of a base.

The pyrimidines represented by the general formula ([l) used in the production and notification of the compounds of the present invention (hereinafter referred to as the method of the present invention) are prepared by dissolving 2,4,6-drialkoxypyrimidine in an organic solvent such as acetone. ．． It can be selectively obtained by hydrolysis with concentrated mineral acids such as hydrochloric acid or tetrahydrobromic acid. Such 4-dialkoxy-6-hydroxypyrimidines such as 2,4-dimethoxy-5-methylthio-6-hydroxypyrimidine, -Cl, 2,
7I-Shedquin-5-methylthio-6-hydroxypyrimidine, 2. /I-physoproboxy5-methylthio-6-hydroxypyrimidine, 2,4-diallyloxy-5-methylthio-6-hydroxypyrimidine, 2,
4-bis(2-propynyloxi7) 5-methylthio-
6-hydroxypyrimidine, 2,4-diphenoxy-5
-methylthio-6-hydroxypyrimidine, 2,4-dibenzyloxy-5-methylthio-6-hydroxypyrimidine, and the like.

In addition, examples of the compound represented by formula (111) that can be used as other raw materials include dimethyl chlorophosphate, diethyl chlorophosphate, ethyl chlorothiophosphate, and the like.

The method of the present invention is carried out in an organic solvent, and the organic solvents used include ketones such as acetone and methyl ethyl ketone, nitrites such as acetonitrile and propionitrile, v/yne, l-/renine, xylene, etc. Examples include hydrocarbons such as tetrahydrofuran, dioxane, diethyl ether, dimethylformamide, dimethyl sulfoxide, and other polar solvents.

In addition, as bases, inorganic salts such as sodium carbonate, botrium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, etc.
l・diethylamide/, ゛pyridine, etc. 0) organic base, or hydrogenated)

In order to carry out the method of the present invention, the amount of 2 mol equivalent to a small amount of "-7" per pyrimidine represented by the general formula (I) is
．． Self-salt, (and 1.5 to 2 moles of 2-11 question formula (Il
l) A halide represented by: Anti) core is) 1
Usually, pyrimidines and a base are dissolved in an organic solvent or (, i
%. This is done by gradually dropping the rogogenide after allowing it to cool down. Reaction. The temperature ranges from 0°C to the boiling point of the solvent, preferably from O'C to room temperature, and one core is generally completed in one to several hours.

After the reaction is completed, the pyrimidines represented by the general formula (I) can be purified by distillation, column chromatography, etc. by carrying out usual post-treatments.

Next, the method for producing the present compound will be specifically explained with reference to a synthesis sequence.

Synthesis example 1, 2,4-dimethoxy-5-methylthio-6
-(0.0-diethylphosphoryloxy)pyrimidine (
Compound number 1) 100υ using a reflux condenser, a thermometer, and a stirrer.
Add 2,4-ditoxy-5-methylthio-6-hydroxypyrimidine (2.09 lQmm
o l) and potassium carbonate 2.89 (20 on
No I) and dimethyl sulfoxide 3QyJ
was added to make Shinshu. Diethyl chlorphosphate 3, Oml
After dropping (21 mmol) at room temperature,
Stir for hours. The reaction solution was drained into water and extracted with ethyl acetate. After washing with water and dehydration, the solvent was removed under reduced pressure.

The crude product was purified by silica gel column chromatography (hegizan:ethyl acetate-1=1) to obtain 2,4-dimethoxy-5-methylthio-6-(0.0-diethylphosphoryloxy)pyrimidine as a yellow liquid.

Yield 2.5g Yield 74% NMR (CDCl2) δ1,46 (61-1, t,
J=7,21(z),2,32(31-1,S),3
．． '98 (31-I, S), 4, 05 (3i-1,
S), 4, 38 ('4 d3J near, 2, 7.2Hz
) Combined 5St example 2. 2,4-Dimethoxy-5-methylthio-6 7-(o,o-diethylthiophosphoboryloxy)pyrimidine (Compound No. 2) 2,11-dimethoxy-5-methylthio-6-( 0.0-diethylthiophosphoboryloxy)pyrimidine was obtained as a colorless liquid.

Yield 73% NM. I also (CCI graduate) δ1,44(6f(,t, J
=7, 2Hz), 2.26(31(,S), 3
, 9 2 (3 11, S), 4.02 (3
11,S), 4.33(41-1,dq,,■=10.
2,7.21(z) Synthesis Example 3,2,' 4-Jethoxy-5-methylthio-6-(0.0-diethylphosphoryloxy)pyrimidine (Compound No. 3) A reflux condenser, thermometer and stirrer were installed. 100nl
2.3 g of 2,4-jethoxy-5-methylthio-6-hydroxypyrimidine (10 m
mc3 1) and triethylamide 7 2J q(2
1 mmol) and 30% tetrahydrofuran.
7nI! ．． was added to make a uniform bath solution. Diethyl chlorphosphate 3, O mI! (2 J mmol) was slowly added dropwise at room temperature, followed by stirring for 1 hour. The reaction solution was drained into water and extracted with ethyl acetate. After washing with water and dehydration, the solvent was removed under reduced pressure.
4-die I・ki/=5-methylf-o6-(0.
0-Diethylphosphoryloki/)pyrimidine was obtained as a colorless liquid.

Yield 2.8 ri Yield 77 Coefficient N1~4R (CC14) δ1,44 (60, t,
J =6,8LIz), 1,47(61(,3J =6
．． 8Hz), 2.28 (31-1, S), /1.29
(/11-1, (Jq, J=6.8.6.8l-Iz
), /1.32(21(,q,J=t3,5Hz),
4.45 (2H, q, J = 6.81 (z) Synthesis Example 42,
4-diynepropoxy-5-methylthio-6-(0,0
-diethylphosphoboryloxy)pyrimidine (compound number 4) 2,4-diynepropoxy-5-
Methylthio-6-(0,0-diethylphosphoryloxy)pyrimidine was obtained as a yellow liquid.

Yield to 70 coefficient N′il:% (CCl q ) δ 1,39 (
1,21-1,d,J=i3,Pak1z),1.40
(61■, 5 J = 7, 2l-1z), 2.23
(3I-I,s), 4. 23 (4I-I; dq, J
=8.4, 7.21(z,), 4.8-5,3(]
, l-J, 1]), 5.1-5, 5 (11-1
,! l]) Synthesis example 5. 2,4-bis(2-propynyloxy)-5-methylthio6-(0,0-diethylphosphoboryloxy)pyrimidine (compound number 5) 2,4-his(2- propenyloxy)
-5-methylthio-6-(0,0-diethylphosphoryloxy)pyrimidine was obtained as a colorless tetrad.

Yield Coefficient 72 NMR (CCItl,) δi, 41. (61(,t
, J = 7, 6l-1z), 2.29 (3 ratio'S
), 2', 38 (], I-1, t, J=2
, Ql-1z), 2.41 (11(t, J=2.0
1lz ), 4.25(4+1, (1(1,''-10,
8,7', 6Hz), 4,87 (21-1,d,
J=2,01lz), 4.99(211d, J=
2.0Hz) The compound of the present invention can be used as insecticidal, acaricidal, or radiocidal rlλ
One festival actually used as an agent is the public/city group liV thing,
Namely, 11 permanent agents, granules, fine granules, powders, aqueous solvents,
It can be formulated into the following forms: aerosol preparations, microcapsule preparations, small steamed coil preparations, preparations impregnated with natural or synthetic substances, concentrated preparations for small amounts of pastry cloth, etc. .

These compositions may be prepared by adding a suitable substance (for example, solid substances such as merck, hentonite, clay, quartzite, vermiculite, etc.) to those known in the art;
As the liquid 113.1, alcohol xylene, kerosene, cyclothexa, cyclohexanone, dimethylformamide, dimethyl sulfoxide, alkylnaphthalene, mineral oil fraction, etc. are used, and if necessary, polyoxyethylene-fatty acid esters, polyoxyethylene- Nonionic and anionic emulsifiers such as aliphatic alcohol ethers, dispersants such as lignin sulfite waste liquor and methylcellulose, carboxyl methylcellulose, natural and synthetic powdered, granular or latex polymers, e.g. Binders such as gum arabic, polyvinyl alcohol, polyvinyl acetate, etc. can be used in the formulation.

Generally, the above compositions have a weight of 0.1 to 95 kg, preferably 0.
．． Contains 5 to 90 parts by weight of active compound.

The compound of the present invention can also be used in combination with one or more known bactericidal agents, ophthalmic agents, acaricides, and nematicides/11j.

Next, the present invention will be briefly explained in detail in the implementation sequence, and the present invention is of course not limited thereto.
It goes without saying that the volume and mixing ratio of additives can be varied within a wide range. stomach.

Formulation Example 1, Emulsion 40 parts of the compound of the present invention and 500 parts or more of alkyl axylene are mixed and dissolved in '·t,q, and diluted with water before use.

Formulation example 2. Permanent agent Compound of the present invention 20 parts Higher alcohol sulfate ester 5 parts Diatomist 70 parts White carbon 5 parts Mix and grind the two ingredients and dilute with water before use.

Formulation example 3, powder Compound of the present invention 3 -i4i1~ Kuruku / + 7’i’11 ni Clay 47 cities White carbon 3 parts The above is mixed and pulverized, and when used, it is directly powdered.

Formulation Example 40 Granules Compound of the Invention 5 parts Hentonite 35 parts 27. After mixing 58 parts of lignin sulfonate and at least 2 parts of lignin sulfonate, the mixture is granulated by adding water, and then granulated and dried to form granules.

Trial: Sprinkle powder obtained from formulation ρ113 on water song seedlings (5-leaf stage) planted in 1° pots of paint using a Pelger duster, then cover with a metal basket.
We lost 10 female adult brown planthoppers each. The test was conducted in triplicate, and the mortality rate was investigated after two days.

Table 1 0, Q-climcl, hylphosphorodi
Thioatc Test Example 2 Into a deep mold/yarn with a diameter of 9C7n and a depth of 10cIL, 200+nl of the diluted emulsion solution prepared in Preparation Example 1 was placed, and 15 final instar larvae of Anonoeca were placed therein.

After being left in a room at 25°C for 48 hours, the mortality rate was investigated. The test was conducted in two series, and the results are shown in Table 2* 0,0
-Diethyl 2.3-clihydro -3-
OXO-2-phenyl-6-pyridaziny
lphosphorot old oate Test Example 3゜The granules obtained in Formulation Example 4 were added to sweet potato knot nematode contaminated soil so that the active ingredient was 50 mg per 11 soil, mixed well, and filled into a pot with a diameter of about 15 mm. . qd
Four tomato seedlings were transplanted into each pot and grown in a greenhouse.

After 40 days, the seedlings were removed to prevent the roots from spreading, and the degree of damage was determined [OI: state in which no root nodules were removed at all (complete control).
The root knot index was determined by evaluating the plant on a five-point scale from ``4'' to ``4'': the most severe state of root knot formation (equivalent to the damage in the untreated area).

Σ (class value x number of individuals) Root knot index-X], 00 Total number of individuals surveyed x 4 The test was conducted in five consecutive runs, and the results are shown in Table 31.

Trial: Inoculate 20 adult Namino mites into each kidney bean seedling with 4゜ double leaves and let it grow for 24 hours. I sprayed it so that it was wet and left it in the greenhouse.

Two days later, insects parasitic on the city were eaten six times, and the percentage of viable roots was calculated.

The test was conducted in triplicate, and the results are shown in Table 71.

Claims (1)

[Claims] (1,) General formula (I) (in the formula, 1te is a lower alkyl group, an alkenyl group, an alkynyl group, phenyl S, 1=t4 hennyl group, Iξ is a lower alkyl group, and X is a lower alkyl group, 5-methylthiopyrimidines represented by (representing an oxygen atom or a sulfuric atom). (2) General formula (Il,) SCII. (In the formula, + and f represent a lower alkyl group, an alkenyl group, an alkynyl group, a phenyl group, or a benzyl group.) In the formula, 1t1 is a lower alkyl group, X is an oxygen atom or a sulfur atom, and H-a1 is a halogen]
- to react with a halide represented by )!
A method for producing 5-methylthiopico-282, represented by the general formula (I) OL(l'' (wherein, R1, 1ton and X have the same meanings as above), having the 111 characters. W is a lower alkyl group, alkenyl group, alkynyl group, phenyl group or benzyl group, 1? is a lower alkyl group, and X is an oxygen atom or a sulfur atom. An insecticide characterized by: