JPS58105956A - Synthesis of organic sulfonic acid thallium (3) salt - Google Patents

Abstract

PURPOSE:To prepare the titled compound useful as a specific oxidizing agent and other reagents, easily and rapidly, suppressing the formation of the by-prodcuts such as thallium (I) salt, by reacting thallic oxide with an organic sulfonic acid in the presence of acetic acid. CONSTITUTION:Finely pulverized thallic oxide is made to react with an organic sulfonic acid (e.g. ethanesulfonic acid) in the presence of acetic acid, and the reaction product is concentrated under reduced pressure until the product becomes viscous liquid. The amount of the organic sulfonic acid is equivalent or slightly excess to thallium (III). The concentrated liquid is mixed with methanol, etc. and left to stand in a refrigerator, etc., and the precipitated crystals are separated by filtration and dried by heating under reduced pressure in the presence of silica gel to obtain the objective compond. The amount of acetic acid is 1-200 equivalent, preferaby 10-100 equivalent to thallium.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention describes thallium(1) salts useful as unique oxidizing and other reagents, particularly thallium(1) organic sulfonates.
).

Thallium (■) salts, such as sulfates, nitrates, acetates, trifluoroacetates, and perchlorates, are compounds useful as unique oxidizing and other reagents. Organic sulfonate (thallium) is similarly effective, but unlike the thallium (1) salt in the above example, it is not as common and is rarely used. The reason for this is believed to be that it is not easy to synthesize thallium (II) organic sulfonate. That is, the thallium salt in the above example can be easily and quickly synthesized by adding an acid to gg2 thallium oxide and reacting it, but in the case of organic sulfonic acids, the reaction is abnormally slow when using the same method. Moreover, there are problems such as a large amount of by-product of thallium (1) salt.

The present inventor has discovered that organic sulfonate thallium (1) can be easily and
In the process of researching a method for rapid synthesis, they discovered that it is effective to carry out the reaction in the presence of acetic acid, and after extensive study, they completed the present invention.

That is, the method of the present invention involves heating thallium oxide and an equivalent amount of organic sulfonic acid to react in an appropriate amount of acetic acid.

I will explain in more detail.

Organic sulfonic acids include, for example, alkyl sulfonic acids such as methanesulfonic acid and ethanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid and naphthalene/sulfonate/
Aromatic sulfonic acids, aralkyl sulfonic acids, alicyclic sulfonic acids, etc. The amount of these sulfonic acids used is preferably equivalent to or slightly in excess of thallium. If the amount is less than the equivalent amount, the thallium side obtained)
The salt becomes a mixture of sulfonate and acetate. A large excess amount is uneconomical, excess sulfonic acid is generally difficult to remove, and therefore it becomes difficult to obtain crystals, and it is not preferable to use the reaction solution as it is.

Acetic acid reacts with thallium oxide, but ultimately becomes thallium sulfonate, and thallium acetate cannot be obtained (if the amount of sulfonic acid is greater than the amount of sulfonic acid).

As a result, acetic acid acts as a reaction promoter. Therefore, the amount used greatly affects the reaction speed.

Naturally, using a larger amount will result in a faster reaction, but it will be less economical. The appropriate amount of acetic acid to be used should be determined from the following points of view. That is, (1) an amount sufficient to dissolve the generated thallium sulfonate (1) (however, this does not apply unless it particularly affects the reaction)
. (b) An amount that provides an appropriate or desired reaction rate.

(c) Economical quantity (including concentration for obtaining crystals, etc.)
. It is. Note that this reaction requires the presence of an appropriate amount of water, and the amount of water also affects the reaction rate. Therefore, an appropriate amount of water should be added to the above amount of acetic acid. Specifically, equivalent to 200 equivalents to thallium, preferably 1O to 1
00 equivalents are common. For reference, a suitable amount of water is about 10 to 30 weight percent/acetic acid.

Secondary oxidized talin (preferably finely ground),
The mixture of sulfonic acid, acetic acid and water is heated to an appropriate temperature to speed up the reaction. It is not preferable to react at a low temperature because it takes a lot of time. As the reaction progresses, thallium oxide dissolves, eventually becoming a nearly colorless and transparent solution (crystals may precipitate if the amount of liquid is small). After the reaction is complete, if necessary, some insoluble matter is removed by filtration, and if there is no problem, the solution is used as is for the next use. If the presence of acetic acid and water poses a problem, it is preferable to ``evaporate to dryness and dry, and use the resulting solid as it is or by dissolving it in a suitable solvent. If it is desired to obtain crystals, it is preferable to precipitate the crystals by concentrating, or to crystallize the product by heating and dissolving it in an appropriate solvent after evaporating to dryness.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 Finely powdered thallium oxide 5.8t (12.5mm
ol) ethanesulfonic acid 8.3 f (75 mmol
), acetic acid som and 2 od of water were stirred at 60° C. for 4 hours. A slight amount of undissolved matter was removed by filtration, and the filtrate was concentrated under reduced pressure until it resembled starch syrup. Approximately the same amount of methanol was added to the concentrated liquid and the mixture was left in the refrigerator. The precipitated needle-shaped crystals were filtered and dried under reduced pressure and heat under silica gel. The colorless crystals obtained had a mass of 9.77 (73 cm). By concentrating the filtrate and performing crystallization again, a few more crystals can be obtained.

Example 2 Finely divided thallium oxide 11.5 f (25 mrn
ol'), methanesulfonic acid 14.5 f (150
A mixture of acetic acid and 20 mmol of water was heated to 80° C. and stirred. After the reaction is completed (thallium oxide is dissolved), some insoluble matter is removed by filtration.
The filtrate was concentrated under reduced pressure until it became a thick starch syrup, and approximately the same volume of methanol as the concentrate was added, and the mixture was left in a refrigerator overnight for crystallization. The precipitated crystals were filtered and dried under reduced pressure by heating (first crystal acquisition). Further crystals can be obtained by concentrating the filtrate and recrystallizing it in the same manner.

The results are shown in Table 1. A similar reaction using 20 mt of hydrous methanesulfonic acid at 100 a/ml did not complete even after 20 hours, and the reaction rate was about 60 mt.

Table 1 Example 3 5.8f of finely ground thallium oxide 11.97f of benzenesulfonic acid and 120% of acetic acid containing 15 parts of water
ffi/ was mixed and stirred at 50°C for 4 hours. After completion of the reaction, treatment was performed in the same manner as in the above example to obtain colorless needle crystals 11.
I got Of.

Example 4 Naphthalene sulfonic acid 15 instead of benzene sulfonic acid
．． 1phthaline sulfo/thallium acid (1) 31 , Off was obtained in the same manner as in Example 3 except that 6f was used.

Example 5 In the same manner as in Example 3 except that 12.9i p-)luenesulfonic acid was used instead of benzenesulfonic acid,
-24.0 tons of thallium toluenesulfonate was obtained.

Patent applicant: Asahi Dow Co., Ltd.

Claims (1)

[Claims] A method for synthesizing thallium organic sulfonate (1) by reacting thallium oxide with organic sulfonic acid, the method comprising coexisting acetic acid in the reaction system.