JPS637191B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel method for producing organic divalent tin compounds, and in particular to a novel method for synthesizing divalent tin carboxylate or divalent tin chelate compounds by reacting metallic tin with a corresponding copper compound. be. Organotin compounds with Sn-O-C bonds are 2,
Alternatively, tetravalent compounds are generally known and are used as curing catalysts for silicone resins and urethane resins, stabilizers for vinyl chloride resins, oil-based paint driers, and the like. These compounds are usually synthesized using tin chloride as a starting material and an appropriate deoxidizing agent, but chelate compounds, especially β-diketone chelates and β-ketoester chelates, are difficult to synthesize by hydrolyzing the product. Because it is easily susceptible to oxidation, it is necessary to carry out the reaction in an anhydrous system, making it difficult to synthesize. These synthetic problems are common to divalent and tetravalent tin compounds, but in the case of divalent tin compounds, which have recently attracted attention due to their unique reactivity, there are problems such as preventing the contamination of tetravalent tin. Therefore, the synthesis was more difficult. Therefore, it was thought that if it were possible to industrially synthesize organic divalent tin compounds, which have industrial utility, the utility value could be expanded.As a result of research, we found that organic copper compounds equivalent to metal tin were found. Therefore, we discovered a new method for directly synthesizing organic divalent tin compounds, leading to the present invention. Thus, the present invention is based on the following general formula or The following general formula is obtained by reacting an organocopper compound with metal tin with or [In each of the above formulas, R ₁ is OH, SH, NH ₂ , OR ₄ ,
A C ₁ to C ₂₂ hydrocarbon group with or without a substituent of COOH or COOR ₄ , R ₂ is a C ₁ to C ₁₈
is a hydrocarbon group, R ₃ is a C ₁ to C ₁₈ hydrocarbon group, or
A group represented by OR ₄ , where R ₄ is C ₁ to C ₁₈
The present invention provides a method for producing an organic divalent tin compound, which comprises producing an organic divalent tin compound represented by the following. To explain in more detail, the organocopper compound used in the method of the present invention is [In the formula, R ₁ is a C ₁ to C ₂₂ hydrocarbon, such as OH, SH,
Hydrocarbon group (NH ₂ OR ₄ ) A group that may or may not contain substituents such as COOH and COOR ₄ . ] Copper carboxylate or its chelate represented by [In the formula, R ₂ is a C ₁ to C ₁₈ hydrocarbon group, and R ₃ is a C ₁ to C 18 hydrocarbon group.
It is a C ₁₈ hydrocarbon group or an OR ₄ group. ] These are β-diketones or β-tetoester chelates shown in the following. These compounds can be easily synthesized by reacting copper salts such as copper chloride, copper sulfate, and copper nitrate, copper hydroxide, copper alkoxide, or organometallic compounds corresponding to the formula - in a conventional manner. I can do it. Such compounds include acetic acid, butyric acid,
Monocarboxylic acids such as octanoic acid, isostearic acid, behenic acid, acrylic acid, methacrylic acid, itaconic acid, benzoic acid, toluic acid, cinnamic acid, maleic acid, succinic acid, adipic acid, dimer acid, phthalic acid, trimellitic acid , polyhydric carboxylic acids such as pyromellitic acid, or partial esterified products thereof, hydroxy acids such as glycolic acid, lactic acid, citric acid, tartaric acid, levulinic acid, dibenzophenone dicarboxylic acid, or dibenzophenone tetracarboxylic acid. amino acids such as ketocarboxylic acids, glycine, alanine, phenylalanine, leucine, aspartic acid, glutamic acid, lysine, cystine, methionine, serine, threonine, p-
Methoxycinnamic acid, p-ethoxybenzoic acid, 4-
Examples include compounds synthesized from alkoxycarboxylic acids such as methoxybutyric acid. Also, in the − expression,
Examples include compounds synthesized from β-diketones such as acetylacetone, dibenzoylmethane, and benzoylacetone, and β-ketoesters such as methyl acetoacetate and ethyl acetoacetate. The reaction between these organocopper compounds and metal tin is CuX ₂ +Sn→SnX ₂ +Cu (-formula) [CuX ₂ is or an organocopper compound corresponding to the formula,
or SnX ₂ represents an organic tin compound corresponding to the formula] This reaction is considered to be a ligand exchange reaction. When synthesizing organic divalent tin compounds through this reaction,
As with the synthesis of alkyl tin, it is advantageous to increase the reaction rate by increasing the contact area of the reaction reagent, so it is desirable to use metal tin in the form of foil or powder. Foil formation or powder formation can be carried out by conventional methods. Alternatively, the organic copper compound of formula - may be reacted directly, but in order to make the reaction more uniform, a solvent such as benzene, toluene,
Hydrocarbons and halogenated hydrocarbons such as xylene, decalin, cyclohexane, n-hexane, petroleum ether, trichlene, perchlorooctane, chlorobenzene, alcohols such as methanol, ethanol, isopropanol, octator, dibutyl ether, tetrahydrofuran, dioxane, etc. ether, acetic acid, butyric acid, octanoic acid, butyl acetate, diethyl adipate, dimethyl phthalate,
It is preferable to use a solvent selected from esters such as methyl acetoacetate and ethyl acetoacetate, and acetylacetones. Since the reaction (-formula) of the present invention is considered to be a ligand exchange reaction, the reaction can be carried out at room temperature, but in order to complete the reaction in a shorter time, it is desirable to heat the reaction. However, the divalent tin compound produced is
If the temperature exceeds 150℃, separation will become severe, so
It is advantageous to carry out the process at temperatures below 160°C, especially below 150°C. The reaction time varies depending on the type of organic group, temperature, solvent, and other factors, but it can be substantially completed in about 30 minutes to 20 hours. The organic divalent tin compound produced by the reaction can be easily and purely isolated by distillation or recrystallization, and the copper powder produced at the same time can be recovered and used as a raw material for synthesizing the organocopper compound. According to the method of the present invention, it is difficult to handle, and
There is no need to use anhydrous tin dichloride or tin dialkoxide as starting materials, which are difficult to synthesize, and the reaction can be performed starting from a copper compound and metal tin, which can be easily synthesized with high yield and high purity. Since the obtained product is of high quality, it is industrially effective as a raw material for resin curing catalysts, organic reaction catalysts, and inorganic materials. Examples of the present invention are shown below. Example 1 Equipped with a thermometer, reflux condenser and airtight stirrer
Weighed 9.6 g of tin powder ground into 28-100 meshes, 11.5 g of Cu (C ₅ H ₇ O ₂ ) ₂ and 100 ml of xylene into a 200 ml four-necked flask, heated to 130°C with stirring, and heated at the same temperature. The reaction was completed after 2 hours of reaction. After the reaction product was cooled to room temperature, unreacted tin and copper precipitated by the reaction were separated using a glass filter, and the resulting liquid was distilled under reduced pressure to remove xylene. When 50 ml of n-hexane was added to the residue and stirred, a small amount of greenish-blue insoluble matter precipitated, which was further separated. Analysis revealed that this precipitate was unreacted Cu(C ₅ H ₇ O ₂ ) ₂ and weighed 0.3 g. The n-hexane solution from which unreacted substances had been removed was distilled at normal pressure to remove n-hexane, and the remainder was distilled under reduced pressure to obtain 12.5 g of a colorless transparent liquid with a temperature of 85-89°/1.5 mmHg. The analytical values of the product were Sn; 37.4%, C; 38.0%,
H: 3.10%, O: 19.97%, Sn(C ₅ H ₇ O ₂ ) ₂
Analysis value of Sn: 37.94%, C: 38.38%, H: 3.23%,
It was confirmed to be Sn(C ₅ H ₇ O ₂ ) ₂ because it was in good agreement with O; 20.45%, and the yield was 88.7%. This product is the result of infrared analysis.

It is shown by [Formula]. Example 2 In the same manner as in Example 1, 3.6 g of tin powder of 28 to 100 meshes, 5.3 g of Cu (OCOCH ₃ ) ₂ , and 100 g of acetic anhydride were added.
ml was weighed into a flask and reacted at 125-130°C for 10 hours, and then filtered at the same temperature to separate unreacted tin and produced copper. The liquid was concentrated by distillation and then recrystallized from acetic acid to obtain 5.2 g of a white powdery solid. As a result of analyzing the product, Sn; 49.60%, C;
20.04%, H; 2.18%, O; 27.55%, Sn
Sn calculated as (OCOCH ₃ ) ₂ ; 50.13%, C;
20.29%, H; 256%, O; good agreement with 27.03%,
The reaction yield was 70% calculated from Cu(OCOCH ₃ ) ₂ . Example 3 In the same manner as in Example 1, 3.6 g of tin powder of 28 to 100 meshes,

7.6 g of [Formula] and 100 ml of ethylene glycol dibutyl ether were charged and reacted at 120°C for 7 hours, unreacted tin and produced copper were separated, and the solvent was distilled under reduced pressure. N-hexane was added to the concentrated solution, stirred, filtered again, the obtained solution was concentrated, cooled to precipitate an amorphous solid, and overdried to obtain 6.9 g. As a result of analyzing the product, Sn; 39.28%, C;
24.41%, H; 3.17%, O; 32.66%, Calculated value as Sn; 39.99%, C; 24.27%, C;
There was good agreement with 24.27%, H: 3.4%, O: 32.34%.

Claims (1)

[Claims] First-order general formula or The following general formula is obtained by reacting an organocopper compound with metal tin with or [In each of the above formulas, R ₁ is OH, SH, NH ₂ , OR ₄ ,
A C ₁ to C ₂₂ hydrocarbon group with or without a substituent of COOH or COOR ₄ , R ₂ is a C ₁ to C ₁₈
is a hydrocarbon group, R ₃ is a C ₁ to C ₁₈ hydrocarbon group, or
A method for producing an organic divalent tin compound, which comprises producing an organic divalent tin compound represented by OR ₄ , wherein R ₄ represents a C ₁ to C ₁₈ alkyl group.