JPS62270566A - 1,2,4-triazolin-5-one derivative and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I (R is lower haloalkyl; with the proviso that a case where R is difluoromethyl is omitted). EXAMPLE:1-( 2-Fluoro-5-nitrophenyl )-3-methyl-4-(1,1,2,2-tetrafluoroethyl)-DELTA<2>-1,2,4- triazolin-5-one. USE:An intermediate for producing agricultural chemicals. PREPARATION:A compound shown by formula X is reacted with a compound shown by formula IX (R<2> is lower alkyl; A is O or S) under heating, then subjected to ring closure reaction in the presence of a base and further reacted with a compound shown by the formula R-Z (Z is Cl, Br or I) to give a triazolinone shown by formula II (R<1> is lower haloalkyl), which is reacted with equimolar amount or excess amount of 1.0-2.0mol based on the triazolinone of a compound shown by the formula M.F (M is alkali metal) in an inert solvent such as dimethyl sulfone, etc., under heating at 50-250 deg.C for 0.5-10hr to give a compound shown by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides: (1) 1 represented by the general formula (I): (wherein, R represents a lower haloalkyl group, except when R is a difluoromethyl group);
2.4-) Riazolin-5-one derivatives and (1) - A method for producing a triazolin-5-one derivative represented by the general formula la): (wherein R1 represents a lower...roalkyl group).

The compound represented by the general formula ti+ of the present invention is a new compound that has not been described in any literature, and is suitable for agricultural chemicals, such as JP-A-60-255.
It is a useful intermediate for producing the compounds described in Publication No. 780, etc. The present invention also provides a method for producing a compound represented by general formula (Ia).

For example, the manufacturing method of the present invention can be diagrammatically expressed as follows.

fllll (Ia)
(1,1 (wherein R and R1 have the above meanings and M represents an alkali metal atom). That is, a compound of the general formula (ml) and a compound of the general formula fII
) A compound represented by general formula (1) or general formula (Ia) can be produced by reacting with a compound represented by formula (1) or (Ia) in an inert solvent.

The alkali metal atom corresponding to M in the compound represented by the general formula flTl includes Na, K, Cs, and Rh.

Alkali metal atoms such as Li can be mentioned.

Examples of inert solvents that can be used in the present invention include sulfur-containing solvents such as dimethyl sulfoxide, dimethyl sulfone, and sulfolane, dimethyl formamide, dimethyl acetamide, Amide solvents such as N-methylpyrrolidone can be mentioned.

Since the reaction of the present invention is an equimolar reaction, each reaction component can be used in equimolar amounts, but it is also possible to use an excess of the compound represented by the general formula (I[), in which case it is preferred. It is preferable to use 1.0 to 2.0 times the mole amount.

The reaction of the present invention generally proceeds under heating at a temperature of 1 to 250°C, for example, 50°C to 250°C.

The reaction time may be appropriately selected from the range of 5 to 10 hours.

After the reaction is completed, the target product can be collected by treating the reaction solution in a conventional manner.

Representative examples of the compound represented by general formula (Il or general formula (Ia)) are shown below.

The compound represented by the general formula (■) of the present invention can be produced by the following method.

(■) (■) ([1 (wherein, R and R1 are the same as above, R- may be the same or different and represent a lower alkyl group, A represents an oxygen atom or a sulfur atom, Y may be the same or different and represent a halogen atom, and Z represents a chlorine atom, a bromine atom, or an iodine atom.) That is, the compound represented by the general formula (III) is
A compound represented by the general formula 00 and a compound represented by the general formula (2) are reacted under heating in an inert solvent to obtain a compound represented by the general formula (2), and the compound is isolated or not isolated.1. Then, a ring-closing reaction is performed in the presence of a base to obtain a compound represented by the general formula, and the compound and the general formula (Fi'l
, (V) or (to), the desired compound can be obtained.

Practical example M 1 1-(2-fluoro-5-nitrophenyl)
-4-difluoromethyl-3-methyl-Δ! 1.2.4
-) Preparation of riazolin-5-one (compound AI) 1.45jF ((10048 mol) of 1-(2-chloro-5-nitrophenyl)-4-difluoromethyl-3-
A mixture of methyl-Δl”-1,2,4,-triazolin-5-one, 1.5p of anhydrous potassium fluoride, and 30-g of dimethyl sulfoxide was heated and stirred at 150°C for 2 hours. After the reaction was completed, the reaction The liquid was cooled to room temperature, poured into ice water, and the desired product was extracted with ethyl acetate.The extract was washed with water, dried, and ethyl acetate was distilled off under reduced pressure to obtain 0.97% of the desired product.

m, p, 99.5°C Yield 70% The following reaction was carried out in the same manner as in Example 1. The results are shown in Table 2.

Table 2 Example 4 1-(2-fluoro-5-nitrophenyl)
-3-Methyl-4-(1,1,2,2-tetrafluoroethyl)-Δ! -1,2,4-) riazolin-5-one (compound 2)! 1-(2-chloro-5) of LOda (0,0085 mol)
-nitrophenyl)-3-methyl-4-(1,1,2,
2-tetrafluoroethyl)-Δ鵞-1,2,4-)riazolin-5-one, (159) (0,0102 mol)
A mixture of anhydrous potassium fluoride and 50% dimethyl sulfone was heated and stirred at 200° C. for 1 hour to carry out a reaction.

After the reaction was completed, the reaction solution was cooled to room temperature, poured into ice water, and the target product was extracted with ethyl acetate. After washing the extract with water and drying, the solvent was distilled off under reduced pressure to obtain an oil. This oil crystallizes when left at room temperature. The obtained crystals are re-crystallized to obtain the target object 2.445
I got +.

m, p, 8G, 7°C, yield 85% The following reaction was carried out in the same manner as in Example 4. The results are shown in Table 3.

Table 3

Claims (2)

[Claims] (1) General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^ represents a lower haloalkyl group.However, except when R^ is a difluoromethyl group.) 1,2,4-triazolin-5-one derivatives represented by: (2) General formula (III): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) (In the formula, R^1 represents a lower haloalkyl group.) Triazolinones and general formula (II): M・General formula (I a) characterized by reacting with a compound represented by F(II) (in the formula, M represents an alkali metal atom): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I a) A method for producing a 1,2,4-triazolin-5-one derivative represented by (wherein R^1 is the same as above).