JPS62167757A - Production of bisarylthioalkane - Google Patents

Abstract

PURPOSE:The reaction of a disulfonate of an alkylene diol or a dihaloalkane with a thiophenol bearing a hydroxyl group readily and inexpensively gives a compound which is used as a recording material, especially as an additive for thermosensitive recording materials. CONSTITUTION:The reaction of a disulfonate of an alkylene diol or a dihaloalkane with a thiophenol bearing an aromatic hydroxyl group is carried out in a solvent such as acetonitrile in the presence of a base such as sodium hydroxide at 50-100 deg.C to etherify the remaining aromatic hydroxyl whereby the objective compound is obtained. It is preferred to use, in this process, 1mol of the dihaloalkane or diol disulfonate, 2-4mol of the thiophenol and 2-6mol of the base.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention This invention relates to a process for producing bisalkoxyarylthioalkanes useful as additives for recording materials, particularly heat-sensitive recording materials.

(Prior Art) In the production of thioether compounds using thiophenol derivatives, particularly alkoxythiophenols, as raw materials, alkoxythiophenols are difficult to obtain or are expensive, making it difficult to use them industrially.

(Object of the Invention) Therefore, the object of the present invention is to provide thiophyl Z/- having an OH group.
It is an object of the present invention to provide a method for producing bisalkoxyarylthioalkaline which is inexpensive and simple.

(Misappropriation of the Invention) The present invention is directed to disulfonic acid esters of alkylene diols and dihaloalkanes. This was achieved by a method for producing bisarylthioalka/, which has the W characteristic of reacting a thiophenol containing the same compound and etherifying the remaining aromatic hydroxyl group.

The method of the present invention can be expressed as a reaction formula as follows.

-R2-X R30-Ar 5-R2-8Ar -0Ra
(III) However, here R1 is an alkyl group or an aryl group, xh halogen atom, R2fl has 7 carbon atoms
to 10, R3fd alkyl group, aralkyl group, Y represents a halogen atom, a sulfuric acid ester residue, an aromatic sulfonic acid ester residue, or an OH group.

Among these, R1 is preferably an aryl group, particularly,
Phenyl and p-tolyl groups are preferred.

Ar represents a substituted or unsubstituted J-membered or 6-membered aromatic ring consisting of a monocyclic ring or a condensed ring. It may contain oxygen atoms, nitrogen atoms, sulfur atoms, etc. in addition to carbon atoms.

From the viewpoint of raw material availability and handling, benzene rings and naphthalene rings are most advantageous.

R2Fi is a divalent group having a carbon atom number of / to io, and particularly preferred is a linear or branched alkylene, oxaalkylene, thiaalkylene, or alkenylene. Among them, straight-chain alkylenes, oxaalkylenes, polyoxaalkylenes, thiaalkylenes, etc. having less than 10 carbon atoms are excellent in terms of ease of synthesis and ease of product purification.

R31-t Represents an alkyl group or an aralkyl group, and is a straight-chain -! The lintel may be either branched or branched. Particularly preferred are lower alkyl groups having j or less carbon atoms and aralkyl groups having r or less carbon atoms.

Y represents a halogen atom, a sulfuric acid ester residue, an aromatic sulfonic acid ester residue, or an OH group.

In other words, it represents RaYId etherification agent, and specific examples include dimethyl sulfate, diethyl sulfate, methyl iodide,
Examples include, but are not limited to, ethyl iodide, benzyl chloride, methyl tosylate, and ethyl alcohol. In particular, sulfuric acid ester compounds and aromatic sulfonic acid ester compounds are preferred from the viewpoint of easy availability and handling.

In order to obtain the compound represented by the general formula (III) at a low cost and in a simple manner and with a reduced amount of by-products, it is particularly preferable to carry out the reaction without removing the reaction intermediate during the production.

To that end, when carrying out the reaction (!), the method for producing (It)! Q~/! Heating at around 0°C, combined use of a base selected from organic bases such as sodium compounds, potassium compounds, calcium compounds, etc., and solvents such as water, alcohol, halogenated hydrocarbons, aromatic compounds, and polar solvents. It is also permissible to use them together.

Among these, it is convenient to use a sodium or potassium compound as the base and a polar solvent as the solvent.

As the inorganic base, caustic soda, caustic potassium, sodium carbonate, and potassium carbonate are preferable, and caustic soda is particularly useful and is convenient from the viewpoint of waste liquid treatment.

As the polar solvent used in the present invention, a solvent having a hydrophilic group such as ether, carbonyl, sulfonyl, cyano or amide is particularly preferred.

For example, methyl ethyl ketone, acetonitrile, dimethylacetamide, acrylonitrile, N-menalpyrrolidone, hexamethylphosphoramide, sulfolane, cyclohexanone, dimethylformamide, dimethyl sulfoxide, acetone, etc. are preferred, and water-soluble solvents are particularly preferred from the viewpoint of ease of post-treatment. preferable.

These solvents have a solid content concentration of 10% or more, preferably Fi
It is used so that it becomes 20% or more.

Further, it is also preferable to use it together with a small amount of water from the viewpoint of dissolving the inorganic base and sulfonate and preventing the by-product of colored substances. Furthermore, carrying out the reaction under an inert gas atmosphere is also a preferable method from the viewpoint of preventing coloring of the liquid.

Further, in the reaction, crown ether and phase transfer catalyst gold may be used.

The reaction may also be carried out under pressure. Particularly favorable results are obtained when acetone is used as the solvent.

From the viewpoint of reactivity and decomposition of the sulfonic acid ester, the reaction temperature is preferably ao 0c or more and izo 0c or less, and particularly preferably zo0c or more and 1000C or less.

The amount of the base used in the present invention is preferably λ to t mol, particularly preferably 2 to 6 mol, per mol of the dihaloalkane or diol disulfonic acid ester.

The amount of thiophenols used in the present invention is preferably 2 to ≠ mol, particularly preferably 2 to 3 mol, per 17 moles of diol disulfo/acid ester.

When a halide or an ester compound is used as an etherification agent in the present invention, the base may be added at the same time as the etherification agent is added, or all necessary amounts may be added at the time of the first addition of the base. It is preferable to add all the necessary amounts of bases in advance.

When alcohol is used as the etherification agent, it is preferable to use all catalysts, and acid catalysts are particularly preferable.

For example, sulfuric acid, hydrochloric acid, aromatic sulfonic acid, sulfonic acid chloride, boron trisulfide or 7tFi aluminum chloride are preferred.

The same solvent as used in reaction (1) can be used.

The amount of the etherifying agent used in the present invention is preferably 7 to 3 moles, particularly preferably 7 to 2 moles, per mole of thiophenols.

(Example of Mima) Example 1 With a stirrer on, 100 ml of acetonitrile, 1 mol of /, λ-p-tolylsulfonyloxyethane, and 0.22 mol of monothiohydroquinone were added to a flask. Take the culm. From the stirrer, the internal temperature of 005 mole equivalent of pr weight % aqueous solution of caustic powder is 7! The solution was added while being careful not to exceed oC. Then, the mixture was stirred for 3 hours under reflux. To this reaction mixture, 0.22 mol of dimethyl sulfuric acid was added dropwise and stirred while refluxing for an additional 30 minutes. The reaction mixture was poured into ice water to precipitate the crystals, which were then recrystallized from methanol/ethyl acetate treated with P.

-monobis(4cm methoxyphenylthio)ethane (mp
lor-10”).

Example 2 In place of l, λ-p-tolylsulfonyl-Φ thiane in Example 1, 1. 1. A reaction was carried out in the same manner as in Example 1 using p-tolylsulfonyloxybutane. ≠−
Bis(4cm methoxyphenylthio)butane (mp10
Cor 3°) got it.

Next, specific examples will be shown, but the present invention is not limited to these.

1)/, J-bis(≠-methoxyphenylthio)ethane 2)/, 2-bis(Hiro-ethoxyphenylthio)ethane a)/, 2-hyx(j-methoxyphenylthio)ethane 4)/, 2-his(3-ethoxyphenylthio)ethanes) i, 3-hy, x, (≠-phthoxyphenylthio)propanely l, ≠-bis(≠-methoxyphenylthio)butane 7)/, a- his(≠-ethoxyphenylthio)butanes)1. ≠-bis(3-methoxyphenylthio)butane9)/! -His(λ-methoxyphenylthio)butane, etc.

Claims (1)

[Claims] A method for producing a bisarylthioalkane, which comprises reacting a disulfonic acid ester of an alkylene diol or a dihaloalkane with a thiophenol having an aromatic hydroxyl group, and etherifying the remaining aromatic hydroxyl group.