JPS61291548A - Production of aromatic secondary amino compound - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful as an intermediate for medicines, agricultural chemicals, etc., in good yield with suppressed formation of by- products, by reacting an aniline with an alcohol in the presence of a catalyst containing a specific metal oxide and copper (oxide) supported on a carrier. CONSTITUTION:A compound expressed by formula I (X is H, halogen, lower alkyl or lower alkoxy; n is an integer 1-3) is reacted with a compound expressed by the formula ROH (R is alkyl or phenyl) in the presence of a catalyst containing a metal oxide selected from rare earth elements, Co, Al, Be, Mo or Zr and copper or copper oxide supported on a carrier, preferably silica, zolite or sellaite, at 150-400 deg.C temperature to afford the aimed compound expressed by formula II. The molar ratio of the copper (oxide) to the other metal oxide in the above-mentioned catalyst is preferably within 1:0.05-2 range.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing aromatic secondary amino compounds.

That is, the present invention provides an aniline represented by the general formula (I): and an alcohol represented by the general formula (■): ROH (10 (in the formula, R represents an alkyl group or a phenyl group)) and an oxide of a metal selected from rare earth elements, cobalt, aluminum, beryllium, molybdenum, or zirconium. General 20I: (wherein X, n and R have the same meanings as above) characterized by reacting steel or copper oxide with a catalyst supported on a carrier. This invention relates to a method for producing group secondary amino compounds.

It is well known that anilines and alcohols are generally reacted in the presence of various catalysts to form N-alkyl and N-arylates. Page 850.

(1958), concentrated phosphoric acid catalyst method (U.S. Pat. No. 299,151)
1), the alumina catalyst method (Hetsmitsches Centralplat, p. 2579, 1953), and the like. However, in these methods, polymeric tar-like substances are produced as by-products, reducing the yield of the target product, and other undesirable by-products are produced, so improvements have been sought. In order to solve these problems, a manufacturing method using a catalyst in which metallic copper is supported on a silica carrier or a carrier made of silica and a metal oxide has recently been patented (Publication Publication No. 55-9063, Publication No. 60-81153). ), but
These also have problems such as the lifetime of the catalyst and the by-product of N,N-dialkylaniline.

As a result of intensive studies to solve these problems, the inventors found that rare earth elements, cobalt, aluminum,
Aromatic secondary amino compounds can be collected without producing by-products by using a catalyst in which at least one metal oxide selected from beryllium, molybdenum, or zirconium and copper or copper oxide are supported on a carrier. The present invention was completed by discovering that it can be synthesized efficiently.

Examples of the metal oxide supported on the carrier include oxides of rare earth elements, cobalt, aluminum, beryllium, molybdenum, or zirconium, and the molar ratio of copper or copper oxide to other metal oxides is 1:a05. -2 is preferred. As the carrier, silica, zeolite, celite, silica earth, pumice, or activated carbon of a grade commonly used as a catalyst carrier is used, and among them, silica, zeolite, and celite are preferred.

These catalysts are prepared by adding the carrier to an aqueous solution of soluble salts of copper and other required elements (e.g. nitrates, sulfates, chlorides) at room temperature, adding alkali under stirring, and thoroughly washing the resulting precipitate with water. - Obtained by drying and then baking in air or inert gas at, for example, 150 to 500°C for 15 to 6 hours. The product obtained by heating in this manner may be used as is, or if necessary, the temperature may be heated at 100 to 400°
You may use the one reduced with hydrogen gas or methanol.

The catalyst may also be prepared by a method in which copper or a copper oxide is supported on a carrier by a known ion exchange method, and then a metal oxide is supported.

Although the purpose of the reaction in the method of the present invention can be achieved by either a pressure contact method or a gas phase contact method, the gas phase contact method is preferred since the reaction can be carried out continuously.

Further, the molar ratio of alcohol to aniline may be at least α1 times in mole, but is preferably α5 to 10 times in mole.

Further, the reaction temperature is usually selected from the range of 150 to 400'co, and the reaction may be carried out in the presence of hydrogen gas, carbon dioxide gas, argon gas, nitrogen gas, helium gas, etc., depending on the case.

After the reaction is completed, the target compound is obtained by separating the by-produced aqueous layer and fractionating the oil layer.

The aromatic secondary amino compound obtained in this way is
It is useful as an intermediate in the general chemical industry, especially in pharmaceuticals and agricultural chemicals.

The present invention will be explained in more detail below based on Examples, but the present invention is not limited thereto.

Example 1: When Celite 545 is suspended in an aqueous solution of nitrate steel and cerium nitrate (molar ratio 1:1) and sodium carbonate is added, K
The resulting precipitate was thoroughly washed with water, dried at 105°C for a day and night, then calcined at 500°C for 5 hours, and reduced with hydrogen gas to obtain a catalyst. A glass reaction tube for gas phase contact with an inner diameter stm is filled with 1 ton of this catalyst and heated to 250°C.

A mixture of aniline and methanol (molar ratio 1:3) was injected into the evaporator 5 at a rate of &5 f/hr. When the distilled reaction product was analyzed by gas chromatography, it was found that Ani I
The conversion rate was 8110% based on J.N., and the yield of N-methylaniline was 819%.

The yield of N-dimethylaniline was α1LII.

Note) Celite 545 is a trademark of John-Manuel Company, and Celite 545 is a mixture of diatomaceous earth and a small amount of Na*CO.
It is said to have been fired with the addition of s.

Example 2: An experiment was conducted in the same manner as in Example 1, using yttrium nitrate and lanthanum nitrate in place of cerium nitrate in Example 1. The results are shown in Table 1. Example 3: The experiment was carried out under the same conditions as in Example 1, except that the aryls and alcohols were changed to those shown in Table 2. The results are shown in Table 2.

Example 4 A reaction was carried out in the same manner as in Example 3 except that 2-chloroaniline was used as the nianiline, and N-methyl-2-chloroaniline was obtained in high yield.

Example 5: Example 1 except that phenol is used as the alcohol
When the reaction was carried out in the same manner as above, N-phenylaniline was obtained in high yield.

Patent applicant Nippon Nohyaku Co., Ltd. (and 1 other person) Procedural amendment dated August 15, 1985 2. Title of invention: Process for producing aromatic secondary amino compounds 3.
Relationship with the case of the person making the amendment Patent applicant 4, Agent 5, Date of amendment order □ “Voluntary” 6. Subject of amendment Noah, Contents of amendment (1) Submit the entire power of attorney.

(2) [Cu-La
Correct as 0 J f [Cu-Lag's j.

Claims (1)

[Claims] General formula (I): ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, X represents a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkoxy group, and n is 1 to Anilines represented by general formula (II) (in which R is an integer of 3) and general formula (II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (wherein R represents an alkyl group or phenyl group) and alcohols represented by General formula (III) characterized by reacting with an oxide of a metal selected from rare earth elements, cobalt, aluminum, beryllium, molybdenum, or zirconium in the presence of a catalyst in which an oxide of copper or steel is supported on a carrier. : ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) A method for producing an aromatic secondary amino compound represented by (in the formula, X, n and R have the same meanings as above).