JPH05222067A - Production of organotin compound - Google Patents

Abstract

PURPOSE:To obtain an organotin compound by a safe method by producing a tetravalent organic acid derivative having many industrial uses from inexpensive compounds as raw materials. CONSTITUTION:A bivalent tin compound of the formula Sn(O2CR')2 (R' is hydrogen, alkyl or aryl) is reacted with a copper salt of an organic carboxylic acid of the formula Cu(O2CR)2 (R is hydrogen, alkyl or aryl; R and R' are mutually the same or different) to give a tetravalent organic acid derivative of the formula SO(O2CR)2(O2CR')2 (R and R' are as shown above).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a tetravalent tin compound used as a paint drier, a resin stabilizer, a reaction catalyst, a tin oxide film forming material used for electronic materials, optical materials and the like. It is about.

[0002]

2. Description of the Related Art The tetravalent tin organic acid derivative Sn (O ₂ C) is widely used for modifying paints and various polymers, and forming tin oxide films having electronic and optical properties.
Various methods have been proposed for the industrial production of R) ₄ , Sn (O ₂ CR ′) ₂ X ₂ (wherein R and R ′ are hydrogen, an alkyl group, an aryl group, X is a halogen, and an acyloxy group). It is well known that it is implemented.

The method for producing the tetravalent tin organic acid derivative is, for example,
Ang.Chem. 59 233 (1947) in to the SnI ₄ acetic anhydride are reacted under thallium catalyst, it is proposed a method of obtaining acetic acid stannic compounds, Inorg Chem, 3 912 (1964 ) in the first chloride 2
By reacting tin with silver isobutyrate, tetravalent isobutyric acid salt Sn [O
A method for synthesizing ₂ C-CH (CH ₃ ) ₂ ] ₄ has been proposed. Furthermore, J. Orgmetal. Chem, 4 377 (1965) proposes a method of reacting tetravinyl tin (Sn (CH = CH ₂ ) ₄ ) with a carboxylic acid to obtain a corresponding tetravalent tin carboxylate.

In these methods, which have been generally known so far, expensive compounds such as stannic iodide and tetravinyltin are used as raw materials, and consideration for toxicity such as thallium is required. It was necessary to use a catalyst, which was not suitable as an industrial production method. Further, the method using inexpensive stannic chloride as a raw material uses expensive silver carboxylate, and thus is not practical and difficult to carry out.

An object of the present invention is to propose a method for producing a tetravalent tin organic acid derivative, which is industrially widely used, from an inexpensive compound as a raw material by a safe method.

The present inventors have studied the production method and reaction of various compounds such as alkoxides and chelates of metals of Group 4 of the periodic table, published their results, and obtained patents. For example, a new method for producing a stannous chelate compound was proposed and a patent was obtained (Japanese Patent No. 1461985). In this method, stannous acetylacetonate [Sn (O ₂ C ₅ H ₇ ) ₂ ] can be directly produced in good yield by reacting metallic tin with copper acetylacetone.

The present inventors have further studied these methods, and as a result, in place of acetylacetone copper, cupric organic carboxylic acid [Cu (O ₂ CR) ₂ ] and stannous organic acid salt Sn (O 2
If ask ₂ CR _{') 2} and reacted tetravalent organic tin derivative [Sn
(O ₂ CR) ₂ (O ₂ CR ′) ₂ ] (R and R ′ are as described below) was obtained, and it was found that the method is effective as a method for producing a tetravalent tin organic carboxylate, and the present invention was achieved. ..

[0008]

The present invention thus provides a divalent tin compound represented by the general formula Sn (O ₂ CR ') ₂ (wherein R'is hydrogen, an alkyl group or an aryl group), and has the general formula C
An organic carboxylic acid cupric salt represented by u (O ₂ CR) ₂ (wherein R is hydrogen, an alkyl group or an aryl group, and R and R ′ are the same or different from each other) is reacted to give a compound of the general formula Sn (O 2 _Two
And a tetravalent tin organic acid derivative represented by CR) ₂ (O ₂ CR ′) ₂ (R and R ′ are the same as above).

Thus, the present invention is intended to provide a method for producing a tetravalent organic acid tin compound using an inexpensive and safe raw material, and includes the following reactions. That is, it is a reaction of Sn (O ₂ CR ′) ₂ + 2Cu (O ₂ CR) ₂ → Sn (O ₂ CR) ₂ (O ₂ CR ′) ₂ + 2Cu.

To explain the method of the present invention in detail, a tetravalent tin organic acid compound can be synthesized by using a tin acyloxy compound represented by Sn (O ₂ CR ') ₂ as a starting material.

In the above formula of the divalent tin compound, R'represents hydrogen, an alkyl group such as a lower alkyl or higher alkyl group such as a methyl group, an ethyl group and a propyl group, an aryl group such as a phenyl group and the like. For this, stannous acetate is preferably used.

As the copper organic carboxylic acid salt reacted with the divalent tin compound, a cupric salt represented by the general formula Cu (O ₂ CR) ₂ is used. In this formula, R represents hydrogen, an alkyl or aryl group. Examples of the alkyl group include lower alkyl groups such as methyl, ethyl and propyl groups as well as higher alkyl groups having a large number of carbon atoms, and examples of the aryl group include phenyl group. R'in the formula of the tin compound and R in the formula of the copper compound may be the same as or different from each other.

Thus, as the copper compound, an aliphatic carboxylic acid such as formic acid, acetic acid, butyric acid, octanoic acid (caprylic acid), lauric acid, stearic acid or R in the above formula, wherein R is hydrogen or an alkyl group, A cupric salt of an aromatic carboxylic acid such as benzoic acid, which is an aryl group, can be used. This carboxylic acid salt also includes those having other substituents.

As shown in the above reaction scheme, the reaction of the present invention has the same acyloxy groups with respect to 1 mol of Sn (O ₂ CR ') ₂ as a starting material, that is, R = R' and R
Tetraacyloxytin Sn (O ₂ CR) ₄ is obtained by reacting 2 mol of cupric organic acid Cu (O ₂ CR) _{2 in} which R and R ′ are both hydrogen or the same alkyl group or aryl group as each other. When the acyloxy group of the divalent tin compound and the acyloxy group of the cupric organic acid are different from each other, that is, when R and R ′ in the above formula are different from each other, the reaction product is Sn (O ₂ CR) ₂
It becomes a mixed acyloxytin compound of (O ₂ CR ′) ₂ .

These reactions are generally carried out in a solvent. A divalent tin compound and a cupric organic acid salt are dispersed in a solvent, reacted at a temperature at or below the boiling point of the solvent, metallic copper produced as a by-product is filtered off, and the filtrate is distilled to remove the solvent. Then, a tetravalent tin organic acid derivative is obtained. The product can be used as it is or after being purified by a usual method such as recrystallization, adsorption and purification.

As the reaction solvent, aromatic hydrocarbons such as toluene and xylene, esters such as isopropyl acetate, butyl acetate and acyl acetate, and ethers such as ethylene glycol diethyl ether, diethylene glycol dimethyl ether and tetrahydrofuran are generally used. When cupric acetate is used as the cupric organic carboxylic acid, it is also effective to use acetic anhydride, acetic acid or the like and use the same type of organic acid as the solvent.

The time of contact with the reaction may be several hours to several tens of hours. Although the reaction can be carried out in a normal atmosphere, it is also effective to carry out the reaction in an atmosphere of an inert gas such as nitrogen or argon in order to prevent the formation of a tin oxide film and side reactions due to oxygen.

[0018]

[Effect] Thus, in synthesizing the tetravalent tin organic acid derivative, all of the conventionally known methods use a tetravalent tin compound as a starting material, whereas the method of the present invention uses a divalent tin compound. The method of the present invention is well known because it is possible to synthesize a high-quality compound with good yield using a safe and inexpensive raw material, and the copper in the copper compound used as a raw material can be recovered and used. This is an advantageous industrial method that is more practical and has a higher economic value than the method.

[0019]

EXAMPLES Examples of the present invention will be shown below. Example 1 In a 200 ml four-necked flask purged with dry nitrogen gas,
Acetic anhydride 150ml as a solvent, stannous acetate 2.48g
(1.05 × 10 ^-2 mol) and cupric acetate 1.96 g
(1.08 × 10 ^-2 mol) was reacted for 2 hours at the boiling point of the solvent. After removing the produced metal copper by hot filtration, the solvent was completely distilled off under reduced pressure, 150 ml of benzene was added to the residue to dissolve it, and the insoluble material was removed by hot filtration again, and the filtrate was concentrated and left to stand. 73 g of white crystals were obtained (yield about 100%). From the melting point, infrared spectrum, and Sn analysis value, this crystal was identified as Sn (OCOCH ₃ ) ₄ .

Example 2 In the same manner as in Example 1, 6.4 g (1.08 × 10 ² mol) of cupric stearate was used instead of cupric acetate.
6.7 g (yield 9
6%) white crystals were obtained. This substance showed Sn (OCOCH ₃ ) ₂ (OC
Was identified as a OC ₁₇ H _{35) 2.}

Claims (1)

[Claims] 1. A divalent tin compound represented by the general formula Sn (O ₂ CR ') ₂ (wherein R'is hydrogen, an alkyl group or an aryl group) and a general formula Cu (O ₂ CR) ₂ (wherein R is Is hydrogen, an alkyl group or an aryl group, and R and R'are the same or different from each other), and a cupric salt of an organic carboxylic acid represented by the formula Sn (O ₂ CR) ₂ (O ₂ CR ') ₂ (R and R '
Is the same as the above), and a method for producing an organotin compound, comprising producing a tetravalent tin organic acid derivative represented by