JP3170900B2 - Method for producing hydroxyl-substituted phenylpyrimidines - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing hydroxyl-substituted phenylpyrimidines useful as intermediates for agricultural chemicals, medicines, organic electronic (liquid crystal) materials and the like.

[0002]

2. Description of the Related Art The production method related to the hydroxyphenylpyrimidines represented by the general formula (I) of the present invention includes:
The following method is described in Khim. Geterotsikl. Soedin., (6), 801-3.

[0003]

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[0004]

However, according to the method disclosed in the above-mentioned literature, the method of synthesizing the compound (a) as a raw material is not always easy, and the compound (b) may be changed depending on conditions.
It is not always satisfactory as an industrial production method, for example, in that (c) is produced and complicated operations are required for separation and purification. For these reasons, the inventors of the present invention have conducted intensive studies on a method for solving the above-mentioned problems, and have found a new industrially advantageous method.

[0005]

That is, the present invention relates to a compound represented by the general formula (II): R-O-A-B-X (II) wherein R is a saturated or unsaturated alkyl group having 1 to 12 carbon atoms. X represents a halogen atom, and -AB
−

[0006]

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A phenylpyrimidine ether represented by the general formula (I) HO-ABX (I) wherein A, B and X have the same meanings as defined above .)
And a method for producing a hydroxyphenylpyrimidine represented by the formula: Hereinafter, the present invention will be described in detail. The above-mentioned phenylpyrimidine ethers (I) are synthesized according to a known method described below.

[0008]

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The phenylpyrimidine ethers (I) include, for example, the following. In the general formula (I), examples of the saturated or unsaturated alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, allyl 2,2-butenyl, 3-butenyl, 2-pentenyl, 3-hexenyl, propargyl,
2-pentynyl, 3-hexynyl, 5-hexynyl and the like are exemplified. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

As the acidic substance, pyridine hydrochloride, pyridine hydrobromide, hydrochloric acid, hydrobromic acid, hydroiodic acid,
Examples thereof include hydrobromic acid-acetic acid, aluminum chloride, aluminum bromide, boron trichloride, and boron tribromide. Among them, pyridine hydrochloride and pyridine hydrobromide are preferred in terms of yield. Boron tribromide is also preferable from the viewpoint of yield. In this case, it is particularly preferable to coexist a salt such as sodium iodide and sodium bromide.

[0011] The amount of the acidic substance to be used is 0.1 to 1 mol of phenylpyrimidine ethers (II) as a raw material.
It is used in an amount of from 1 mol to 50 mol, preferably from 0.3 mol to 30 mol, but of course, more can be used. A solvent can be used in this reaction. These can be used without any particular limitation as long as they are inert to the reaction, but the above-mentioned acidic substances can also be used as a solvent.

The reaction temperature is usually from -10 ° C to 250 ° C, and if necessary, the reaction can be carried out in an autoclave. The reaction time is not particularly limited, and the reaction may be terminated when the raw materials disappear. After completion of the reaction, the reaction solution is poured into, for example, water, and extraction, concentration, recrystallization, chromatographic purification and the like can be performed to obtain the hydroxyphenylpyrimidines represented by the general formula (I).

[0013]

According to the method of the present invention, hydroxyphenylpyrimidines (I) can be produced industrially advantageously. The compound (I) is useful not only as an intermediate for liquid crystal materials but also as an intermediate for medicines, agricultural chemicals and the like.

[0014]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. [Example 1] 2- (4-bromophenyl) -5-ethoxypyrimidine (5 g, 0.018 mol) and pyridine hydrochloride (22 g)
And stirred at 220 ° C. for 30 minutes. After the completion of the reaction, the reaction solution is cooled to 50 ° C., and 50 ml of water is added to precipitate crystals. 100 ml of toluene was added for extraction, and the organic layer was washed successively with 2% hydrochloric acid and water. The organic layer was concentrated under reduced pressure, and the residue was recrystallized from toluene-heptane to give 2-
(4-bromophenyl) -5-hydroxypyrimidine 3.
8 g (85% yield) are obtained.

Example 2 2- (4-chlorophenyl)
5 g (0.02 mol) of -5-propoxypyrimidine and 25 g of pyridine hydrochloride are charged and reacted at 210 ° C. for 3 hours. Thereafter, by post-treatment and purification according to Example 1, 3.4 g (83% yield) of 2- (4-chlorophenyl) -5-hydroxypyrimidine is obtained.

Example 3 2- (4-bromophenyl)
A solution of 3.9 g (0.01 mol) of 5-decyloxypyrimidine, 1.3 g of boron tribromide, 2 g of sodium iodide and 20 ml of dichloroethane is reacted under reflux for 15 hours. After completion of the reaction, the reaction solution was poured into ice, the organic layer was further washed with water, concentrated and purified by column chromatography with toluene / ethyl acetate to give 2- (4-bromophenyl) -5-hydroxypyrimidine 2.3 g (90% yield)
Is obtained.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Naoyuki Takano 2-10-1 Tsukahara, Takatsuki City, Osaka Prefecture Inside Sumitomo Chemical Co., Ltd. (56) References Khim. Geterotsikl. Soedin; (1990) No. 6 p 801-803 (58) Fields investigated (Int. Cl. ⁷ , DB name) C07D 239/34 C07D 239/30 CA (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] 1. A compound represented by the general formula: R-O-A-B-X (II) wherein R represents a saturated or unsaturated alkyl group having 1 to 12 carbon atoms, X represents a halogen atom, and -A -B
-Is Wherein a phenylpyrimidine ether represented by the formula is reacted with an acidic substance: HO-ABX (I) (wherein A, B and X have the same meanings as described above) .)
A method for producing a hydroxyphenylpyrimidine represented by the formula: 2. The method according to claim 1, wherein the acidic substance is pyridine hydrochloride or pyridine hydrobromide. 3. The method according to claim 1, wherein the acidic substance is boron tribromide. 4. The method according to claim 3, wherein sodium iodide is added to boron tribromide.