JPS61251635A - Production of ether - Google Patents

Abstract

PURPOSE:To obtain an ether, by reacting an alcohol with an aromatic sulfonylhalide in a specific polar solvent using an inorganic base selected from hydroxides and carbonates of sodium or potassium as an alkali, and further reacting the resultant sulfonate with a phenol derivative. CONSTITUTION:An alcohol such as phenoxyethanol is reacted with an aromatic sulfonylhalide such as tosyl chloride to obtain a sulfonate, which is further reacted with a phenol derivation such as p-ethylphenol to obtain an ether such as 1-phenoxy-2-p-ethylphenoxyethane; wherein an inorganic base (sodium hydroxide is especially preferred) selected from hydroxides and carbonates of sodium or potassium is used as an alkali and a polar solvent having >=65 deg.C boiling point (example; methylethylketone, acetonitrile, cyclohexane, etc.) is used as a solvent. ¦This process is applicable to an alcohol having an inner ether.

Description

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

(Prior Art) As a method for producing ether using a phenol derivative as a raw material, a method in which a halide is reacted in the presence of an alkali is well known.

However, halides are generally difficult to obtain, and in particular, it has been completely impossible to use halides having an ether bond in the molecule as industrial raw materials.

It has also been attempted to obtain a sulfonate from alcohol in the presence of an organic base such as triethylamine or pyridine, remove the used organic base by recrystallization or the like, and then react it with a phenol derivative.

However, this method also has many problems that need to be resolved, such as the complexity of treating bad odor 1 water with an organic base and the increase in cost due to the complexity of the process.

The present inventors have considered these points, and by using a specific alkali, limited solvent, and reaction temperature]
They developed a method to obtain ether from easily available alcohol without having to separate the sulfonate.

(Object of the Invention) Therefore, the present invention provides a simplified method for producing ether using alcohol as a starting material.

In particular, it has the advantage of being applicable to alcohols having ether in one molecule.

(Structure of the invention) The method of the present invention can be expressed as a general formula as follows.

R10H-1→-1→RIOAζ/)R2SO2XChrysanthemumArOH Especially as R10H, human rOROH is preferable, R25
O2X is preferably aromatic sulfonyl chloride, and kr *Ar is alkoxy, alkyl, alkenyl, acyl, aralkyl, halogen, aryl,
This is the case in the case of an aromatic ring which may be substituted with aralkyl, substituted amino, etc., and the most convenient case is the case with an alkoxy, alkyl, aralkyl, halogen-substituted or unsubstituted benzene ring or naphthalene ring. In this case, the number of carbon atoms in the substituent is preferably about 1 or less, particularly preferably 3 or less.

Examples of aryloxy groups include phenoxy, tolyloxy, xylyloxy, trimethylphenoxy, tetramethylphenoxy, chlorphenoxy, chloromethylphenoxy, fluoromethylphenoxy, p-methoxyphenoxy, 1)-butoxyphenoxy, methoxytolyloxy, and trimethylnaphtho. xy, t-butylphenoxy, p-ethylphenoxy, t-amylphenoxy,
N-dodecylphenoxy, dodecylnaphthoxy, chloronaphthoxy, benzylphenoxy, benzyloxyphenoxy, fluorophenoxy, tetrafluorophenoxy, benzyloxyethoxy, β-phenoxyethoxyphenoxy, etc. are vignetted. More specifically regarding Ar0ROHK, the preferred number of carbon atoms in the alkanol moiety is 1 or less, preferably t or less, and %KFftL< is μ or less.

It may be linear or branched.

As mentioned above, as long as it contains one or more aryloxy groups, it may have any other substituents.

For example, β-aryloxy-substituted alkanol, α-aryloxy-substituted alkanol, r-7 aryloxy-substituted alkanol, δ-7 lyloxy-substituted alkanol, ω-7 lyloxy-substituted alkanol, ω-aryloxy-substituted alkoxy alkanol, aryloxy-substituted Examples include haloalkanols, aryloxy-substituted alkoxyalkanols, and aryloxy-substituted hydroxyalkanols. Among these, β or ω substitution products are particularly preferred.

R25O2X in the present invention is preferably an aliphatic or aromatic sulfonyl chloride.

Specifically, the number of carbon atoms is preferably 16 or less, particularly preferably 7 or less. For example, triisopropylnaphthalenesulfonyl,
Ethylnaphthalenesulfonyl, dimethylnaphthalenesulfonyl, isopropylnaphthalenesulfonyl, naphthalenesulfonyl, o- or uo-)! Examples include chloride such as J sulfonyl, hanzenesulfonyl, /, J-benzenedisulfonyl, methylbenzenedisulfonyl, ethylhexanesulfonyl, methanesulfonyl, methanesulfonyl, and hexanesulfonyl. In particular, toluenesulfonyl chloride is most preferred, and has many excellent features such as reactivity in an inorganic base-polar solvent, no interference with the etherification reaction, and ease of handling.

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

Particularly preferred are polar solvents having a boiling point of 4j'C or higher used in the present invention, and solvents having a hydrophilic group such as ether, carbonyl, sulfonyl, cyano or amide.

For example, methyl ethyl ketone, acetonitrile, dimethylacetamide, acrylonitrile, N-methyl lolidone, hexamethylphosphoramide, sulfolane,
Cyclohexanone and the like are preferred, and % water-soluble solvents are preferred from the viewpoint of ease of post-treatment.

In the method for producing ether in which a halide is reacted in the presence of an alkali, dimethylformamide and dimethyl sulfoxide are preferred in the present invention.
It didn't give good results.

These solvents have a solid content concentration of 10 or more, preferably 20
It is used so that it is 0 or more.

In addition, an inorganic base, X, can also be used in combination with a small amount of water.

This is preferable from the viewpoint of dissolving the phonate salt 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 coloration of the liquid.
Crown ethers and phase transfer catalysts may also be used.

In particular, in the present invention, due to the reaction between an inorganic base and an active acid halide in a polar solvent, a competitive reaction between the sulfonation reaction and the hydrolysis reaction of the acid halide occurs, leading to a decrease in yield and difficulty in purification. It is easy to invite sadness. From this point of view, it is preferable to control the reaction temperature of the system to /100C or less, and in particular, perform the step of 1-sulfonetation reaction at 70'C or less,
It is desirable to carry out the etherification reaction step at 47'C or higher.

Example ! In a flask equipped with a stirrer, add jOvl acetoni)
Dispense IJA/, 0.1 mole of 7-enoxyethanol and tosyl chloride. While stirring, 1θ, JJ
Add a molar equivalent of arwt@caustic soda aqueous solution dropwise at room temperature, and -2θ while being careful not to exceed the internal temperature +t'c.
Hold for minutes.

Next, 011 mol of p+ ethylphenol was added. Add a small drop, r! ~riz It took me two hours to get to Oc. When the reaction mixture was allowed to cool and was poured into a methanol-water mixed solvent, crystals precipitated, and the purity was determined by liquid chromatography to be more than 100%, and the melting point was 1oy-1'C. p-ethylphenoxyethane was obtained. Yield: 6 cm.

Examples 2 to 5 When methyl ethyl ketone, N-methylpyrrolidone, hexamethylphosphoramide, or sulfonate was used in place of acetonitrile in Example 1, the desired product was obtained with a yield of 7-7. Especially when N-methylpyrrolidone, hexamethylphosphoramide and sulfolane are used, p-
It was found that the reaction was completed by simply stirring for about 10 minutes after adding ethylphenol dropwise, which was particularly advantageous.

Example 6 /-phenoxy-col-methoxyphenoxyethane was obtained in the same manner as in Example 1 except that ethylphenol was replaced with p-methoxyphenol. Yield: 3 cm.

Reference Example/An example of thermal recording paper using ether obtained by the method of the present invention is shown.

Electron-donating colorless dye Ni-anilino-3-o a
-4-jethylaminofluorancho! 1 and 2-anilino-3-methyl-1-N-methyl-N-isoamylaminofluorancho, jp! Tivoli vinyl alcohol (
Ken measure? Polymerization degree: 1ooo) Dispersed with aqueous solution 31P using Su/Domil. On the other hand, it was similarly dispersed in a sand mill together with an aqueous solution of bisphenol hioytzes polyhinyl alcohol, which is an electron-accepting compound.

Furthermore, the etherification reactions obtained in Examples 1 and 6 were dispersed together with 2 polyvinyl alcohol using a horizontal sand mill to obtain a particle size of 2 μm. After mixing these μ species dispersions, kaolin (Jossia kaolin) op was added to disperse well, and then (Ruffin Wax Emuldimine IO
Regret? i (Chukyo Yushi Cellosol Nadako T) a and ry were added to prepare a coating liquid.

The coating solution was applied onto neutral paper having a basis weight of 10/12 so that the solid content coating amount was z, a1p/m2, and 6
After drying at 0'C for 1 minute, a coated paper was obtained by applying a suit calender with linear pressure toKIIW/Sono.

The coated paper is sent to the facsimile machine, and the heating energy is sent to the fax machine.
/lx'' to determine the color density.

The results are shown in the table below.

This table also shows that the ether according to the method of the present invention is useful for improving sensitivity.

Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendment Worker 1. Indication of the case: 1985 Patent Application No. 933λR No. 2, title of the invention: Process for producing ether 3, person making the amendment Relationship with the case: Patent applicant Location: 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name: (52) Fuji Photo Film Co., Ltd. Date of amendment order: July βρ, Showa tσ (shipment date) & Target of amendment: Statement a Contents of the amendment We will submit an engraving of the detailed statement (with no changes to the content).

Claims (1)

[Claims] Alcohol is reacted with an aromatic sulfonyl halide in the presence of an alkali to obtain a sulfonate, and then reacted with a phenol derivative using an inorganic base selected from sodium or potassium hydroxide or carbonate as the alkali, A method for producing ether, characterized in that a polar solvent with a boiling point of 65° C. or higher is used as a solvent.