JPS59122468A - Preparation of 2-methoxy-6-methylaminopyridine - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 2-methoxy-6-methylaminopyridine.

2-Methoxy-6-methylaminopyridine is a compound useful as an intermediate for pharmaceuticals, agricultural chemicals, and the like.

The present inventors have already proposed a method for producing 2-halo-6-medoxyviridine by reaction with methylamine.

Furthermore, the inventors conducted various tests and conducted extensive studies, and as a result 2
- It was discovered that by reacting halo-6-medoxypyridine with methylamine in the presence of copper or a copper compound, 2-methoxy-6-methylaminopyridine can be produced in high yield by suppressing the formation of by-products. To complete the invention, the present invention is expressed by the general formula @・鵠@2-halo6-
2-Methoxy-6 characterized by reacting medoxypyridine with methylamine in the presence of copper or a copper compound
- A method for producing methylaminopyridine is provided.

In the present invention, copper or a copper compound is used. Examples of copper compounds include inorganic acid salts such as copper sulfate, copper chloride, and copper nitrate; organic acid salts such as copper naphthenate and copper acetate; and oxides such as copper FiI chloride. , hydroxides such as copper hydroxide, and the like. Metallic copper or copper compounds thereof are usually used in an amount of about 1 to about 50 weights, preferably about 5 to about 60 weights, relative to 2-halomethoxypyridine.

The amount of methylamine used is about 2 to about 20 times the molar amount of 2-halo-6-medoxyviridine, preferably about 2 to about 10 times the molar amount. It is preferable to use a solvent to facilitate the reaction.

The solvent is 2-no-6-medoxypyridine.

Examples include water, benzene, alcohol, etc., which do not react with methylamine but dissolve it.

Methylamine is a gas at room temperature and is usually available as an aqueous solution. Therefore, it is generally convenient to react 2-halo-6-medoxyviridine with an aqueous methylamine solution in the presence of copper or a copper compound. The reaction temperature is about 8
0 to about 150°C, preferably about 100 to about 13
The temperature is 0° C., and the reaction time is suitably about 1 to about 20 hours.

By the method of the present invention, 2-methoxy-6-methylaminopyridine can be obtained in high yield.

Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 200m/! 2-chloro-6-medoxyviridi 7 and cuprous chloride 49r in a magnetically stirred autoclave.

60ml of 40-thimethylamine aqueous solution was taken and reacted at 120°C for 8 hours. After the reaction was completed, the autoclave was cooled, opened, and the reaction solution was taken out. Then 2 in the reaction solution
-Methoxy-6-methylaminopyridine was extracted with ether. The ether extract was dried over anhydrous magnesium sulfate, and the ether was distilled off.

The residue after distilling off the ether was distilled under reduced pressure, and the boiling point was 88-92℃.
/5'' Hg of 2-methoxy-6-methylaminopyridine (14.99r) was obtained. The yield of 2-methoxy-6-methylaminopyridine was 77.5% based on 2-chloro-6-medoxyviridine. Ta.

Infrared absorption spectrum (Nacl) 3420 (-NH), 2950 ((!-H), 1600
゜1475, 1420 (@) cm-' Nuclear magnetic resonance absorption spectrum (CC internal bell quasi TMS) δ
2.86(d)ppn (3H)δ 585
(s)ppm (5H)δ 4.40 pP
I (IH) δ 5.84 (d) ptxn
(IH) δ 544 (d) ppm (I H
) δ 7.12 (t) pTn (I H) elemental analysis (
c7HIo gift 0) The results are as follows: Hunger OHN O Analysis value (%) 60,757.22 2α35 11.
68 theoretical value (@ 60.85 7.i 2[L27
11.58G (! - Molecular weight by MS 168 Example 2 Into the same reaction apparatus as in Example 1, 30g of 2-bromo-6-methoxypyridine and 5 copper sulfate (pentahydrate) 60ml of a 40% methylamine aqueous solution were placed. , and reacted at 100°C for 10 hours.

After the reaction was completed, the same experimental operations as in Example 1 were carried out to obtain 2-methoxy-6-methylaminopyridine 1&49r. 2
-Methoxy-6-methylaminopyridine yield is 2-
It was 74.5% based on bromo-6-medoxyviridine.

Examples 5 to 7 2-chloro-6-medoxyviridine, copper or a copper compound, and a 40% aqueous methylamine solution were placed in the same reaction apparatus as in Example 1 and reacted under the reaction conditions shown in Table 1.

After completion of the reaction, 2-methoxy-6-methylaminoviridine as shown in Table 1 was prepared by the same procedure as in Example 1.Next, compounds obtained from the compounds of the present invention and examples of their use as herbicides will be shown.

1.38 ml of 2-methoxy-6-methylaminopyridine, which is the target substance of the method of the present invention, and the same amount of anhydrous potassium carbonate were stirred at room temperature in 20 m of acetone, and 2 Drt of acetone was added.
2-naphthyl chlorthioforme dissolved in tl
．． 23g was added and after 30 minutes the reaction mixture was extracted with benzene.
Wash with water, dry, and recrystallize to obtain 〇-2-naphthyl N-(6-
2.759 of medoxy 2-pyridyl)-N-methyl-thiocarbamate was obtained.

Melting point 95.5-97°C Elemental analysis (';s H+a N2a2 B) CH
N Analytical value (→ 66.42 4.89 a81 theoretical value ((6) 66.65 4.97 &64
Fill a porcelain pot with a diameter of 9 cm with paddy soil, add water and plow through the soil, sow weed seeds on the surface layer of the soil, and grow 1 c of paddy rice seedlings (variety: Nipponbare) at the 2-leaf stage! Two plants were planted at a depth of n. The next day, the water was flooded to a depth of 2 cm, and 〇-2-naphthyl N-
A wettable powder containing 10% (6-medoxy 2-pyridyl)-N-methylthiocarbamate was diluted in 10 d of water per pot and dropped onto the water surface. Thereafter, the plants were left in a greenhouse and 6 weeks after treatment with the chemical solution, the herbicidal effect and the effects on paddy rice were determined. As a result, the amount of test drug was 125 g/10 a
There is no chemical damage to paddy rice seedlings, and there are nobies and snails.

Controlled 100 fireflies, Japanese fireflies, and Kikashigusa.

Patent applicant: Toyo Soda Kogyo Co., Ltd.

Claims (1)

[Claims] Indicates an atom. A method for producing 2-methoxy-6-methylaminopyridine, which comprises reacting 2-no-6-medoxypyridine represented by (2) with methylamine in the presence of copper or a copper compound.