JPH0774211B2 - Substituted 1,3-dioxane derivative and process for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to various synthetic intermediates for functional materials, pharmaceutical intermediates,
The present invention relates to a substituted 1,3-dioxane derivative having an ether bond in its side chain, which is useful as a high-performance solvent used in the electronics industry and general chemical industry, and a method for producing the same.

2. Description of the Related Art In recent years, heterocyclic compounds, particularly compounds having a cyclic ether structure in one molecule and an ether bond through a methylene group in a side chain, have been used in various applications such as conductivity. It is expected as a necessary functional material, as a display element in the electronic industry field, and as a pharmaceutical intermediate in the pharmaceutical industry field.

Means for Solving the Problems The present invention has been made in response to such a request, and its gist is the general formula [I]: (In the formula, R ₁ represents a C _{2 to} C ₆ perfluoroalkenyl group, and R ₂ and R ₃ each independently represent hydrogen, a methyl or an ethyl group.), And a substituted 1,3-dioxane derivative and a method for producing the same. Exist in.

The substituted 1,3-dioxane derivative represented by the above general formula [I] has the formula [II]: 5-alkyl-5 obtained by dehydration reaction with trimethylolpropane and an aldehyde or a ketone
It can be easily produced by using a hydroxymethyl-1,3-dioxane derivative as a raw material and reacting it with a C _{2 to} C ₆ perfluoroolefin (see the following reaction formula).

The raw material is trimethylolpropane, and formaldehyde, acetaldehyde, propionaldehyde are used as the aldehyde, and acetone, methyl ethyl ketone, diethyl ketone, or the like is used as the ketone.

Further, a long-chain aldehyde may be used, but enlarging the molecule is not a good measure for the function of the compound of the present invention.

When synthesizing an ether having a perfluoroalkenyl group, a C _{2 to} C ₆ perfluoroolefin is used, and among them, one having a side chain is preferable. When reacting with perfluoroolefin, it can be directly reacted at a low temperature in a solvent such as DMF, THF, acetonitrile or diethyl ether using a tertiary amine such as triethylamine or triethylenediamine or an alkali catalyst such as potassium fluoride. .

As perfluoroolefin, perfluoro-2-
Methyl-2-pentene is most preferable, and this can be easily obtained by the method described in JP-B-57-2697.

Hereinafter, the present invention will be described with reference to examples.

Example 1 Synthesis of 2,5-diethyl-5-hydroxymethyl-1,3-dioxane: 1.0 mol (134 g) of trimethylolpropane and 1.1 mol (64 g) of propionaldehyde were used as catalysts with 0.2 g of p-toluenesulfonic acid. Using 300 ml of benzene as a solvent, a flask equipped with a stirrer equipped with a Dean-Stark distiller was charged, and the mixture was stirred for 2 hours while azeotropically removing water produced while refluxing. Anhydrous potassium carbonate was added to the reaction mixture to neutralize it, and after the salt was separated after drying, benzene was distilled off from the liquid, followed by vacuum distillation at 77 to 79 ° C / 0.2 mmHg.
162 g (yield 93%) of a distillate was obtained.

Synthesis of 2,5-diethyl-5- (perfluorohexenyl) -oxymethyl-1,3-dioxane: 2,5-diethyl-5-hydroxymethyl-1,3-dioxane 0.5 mol (87 g) obtained by the above method was taken in a condenser of 1, 300 ml of acetonitrile as a solvent, a four-necked flask equipped with a stirrer, 0.5 mol (51 g) of triethylamine was added, and 0.5 mol (1 mol) of perfluoro-2-methyl-2-pentene was added while cooling while paying attention not to exceed 25 ° C below room temperature.
50 g) was gradually added dropwise, and after completion of the addition, stirring was continued for 2 hours to complete the reaction, and the reaction solution was extracted with ether and treated with an aqueous sodium bicarbonate solution. Wash thoroughly with water, dry over anhydrous magnesium sulfate, evaporate the excess solvent, and distill under reduced pressure to 70 ° C /
A fraction of 189 g (yield 83%) of 0.7 mmHg was obtained. The physical properties of the product are shown in Table-1.

From the gas chromatogram, it was confirmed that the product was a single product of 99.5% or more, and it was confirmed from the infrared absorption spectrum that the characteristic absorption of OH had completely disappeared, and elemental analysis was performed. The results were as follows.

Elemental analysis: as C ₁₅ H ₁₇ O ₃ F ₁₁ (calculated value) C: 39.43% (39.41%) H: 3.68% (3.76%) F: 45.84% (45.80%) Example 2 2,2-Dimethyl-5 -Ethyl-5-hydroxymethyl-
Synthesis of 1,3-dioxane: 1.0 mol (134 g) of trimethylolpropane and acetone 2
Mol (116 g) was charged to 0.5 g of p-toluenesulfonic acid as a catalyst and 300 ml of benzene as a solvent in a flask equipped with a stirrer equipped with a Dean-Stark distiller. The mixture was stirred for 3 hours while being removed. Anhydrous potassium carbonate was added to the reaction mixture to neutralize it, and after drying, salts were filtered off, benzene was distilled off from the filtrate, followed by vacuum distillation, and a fraction of 153 g at 78 to 80 ° C / 0.2 mmHg.
(88% yield) was obtained.

Synthesis of 2,2-dimethyl-5-ethyl-5- (perfluorohexenyl) -oxymethyl-1,3-dioxane: 2,2-dimethyl-5-ethyl-5-obtained by the above method
Hydroxymethyl-1,3-dioxane 0.50 mol (87 g) and perfluoro-2-methyl-2-pentene 0.5 mol (150
g) was reacted in the same manner as in Example 3 and then purified to give 7
196 g (yield 86%) of a fraction of 6 ° C./5 mmHg was obtained. The physical properties of the product are shown in Table-1.

From the gas chromatogram, it was confirmed that the product was a single product of 99.5% or more, and it was confirmed from the infrared absorption spectrum that the characteristic absorption of OH had completely disappeared, and elemental analysis was performed. The results were as follows.

Elemental analysis: As C ₁₅ H ₁₇ O ₃ F ₁₁ (calculated value) C: 39.41% (39.49%) H: 3.73% (3.76%) F: 45.76% (45.80%) EFFECTS OF THE INVENTION The compounds according to the present invention have a heterocyclic structure in the molecule that gives various functions, and are all stable compounds insoluble in water. Moreover, it can be used as a solvent in a wide temperature range. Although the molecule itself is not particularly polar, it has a structure that easily forms an ether bond through the methylene group of the side chain and a coordination center because the 1,3-dioxane ring is a 6-membered ring. By utilizing three oxygen loan pairs, the characteristic property of having the ability to promote cations can be utilized as various functional materials.

Claims (4)

[Claims] 1. A general formula [I] A substituted 1,3-dioxane derivative represented by the formula: wherein R ₁ represents a C _{2 to} C ₆ perfluoroalkenyl group, and R ₂ and R ₃ each independently represent hydrogen, a methyl or an ethyl group. 2. A first which is 2,5-diethyl-5- (perfluorohexenyl) -oxymethyl-1,3-dioxane.
The derivative according to the item. 3. A derivative according to claim 1, which is 2,2-dimethyl-5-ethyl-5- (perfluorohexenyl) -oxymethyl-1,3-dioxane. 4. A compound represented by the general formula [I]: wherein two methylol groups of trimethylolpropane are dehydrated with an aldehyde or a ketone to form a cyclic acetal, and the remaining methylol group is perfluoroalkenyl etherified. [Wherein R ₁ represents a C _{2 to} C ₆ perfluoroalkenyl group, and R ₂ and R ₃ each independently represent hydrogen, a methyl or an ethyl group], and a method for producing a substituted 1,3-dioxane derivative.