JPS60228474A - 2-(4'-perfluoroalkenyloxyphenyl)-4-isopropyl-5,5-dimethyl-1,3-dioxane and 2-alkyl-substitution product and preparation thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (Rf is 2-20C perfluoroalkenyl; R is H or alkyl). EXAMPLE:2-Methyl-2-( 4'-perfluorononenyloxyphenyl )-4-isopropyl-5,5-dimethyl-1,3- dioxane. USE:An additive for ink media, particularly special ink, e.g. high-speed recording ink jet, base for functional fluids, e.g. lubricating oil, insulation oil, particularly transformer oil, cable oil and breaker oil and further a surface modification additive for plastics to improve lubricity, heat resistance and light resistance of plastic surfaces. PREPARATION:2,2,4-Trimethyl-1,3-pentanediol and a p-perfluoroalkenyloxybenzaldehyde or p-perfluoroalkenyloxyphenyl alkyl ketone are subjected to azeotropic dehydration in the presence of an organic solvent to give the aimed compound expressed by the formula.

Description

Detailed Description of the Invention The present invention provides novel 2-(4'-perfluoroalkenyloxyphenyl)-4-inpropyl-5,5-dimethyl-1,3-dioxane, its 2-alkyl substituted products and its Regarding the manufacturing method.

Since the above compound has a perfluoroalkenyl group,
A stable liquid substance that maintains high fluidity and is insoluble in water - Ink media - Especially additives for special inks such as high-speed recording ink jets, lubricating oils, insulating oils, especially transformer oils, cable oils, and shielding oils. It can be used in various fields such as base for oil and other functional fluids. Furthermore, by adding it to general-purpose plastics, it can be used as a surface-modifying additive for plastics that improves the lubricity, heat resistance, and light resistance of the plastic surface.

The compound of the present invention comprises 2,2.4-)dimethyl-1,3-bentanediol and P-perfluoroalkenyloxybenzaldehyde or P-perfluoroalkenyloxyphenylalkyl ketone, preferably in an organic solvent in the presence of an esterification catalyst. It can be easily obtained by dehydration reaction.

2,2.4-)dimethyl-1,3-bentanediol, which is a raw material, has two hydroxyl groups in positions suitable for forming a cyclic acetal from a steric structure, and the compound of the present invention can be produced in high yield. However, the cyclic acetal produced from this structural feature provides a characteristic hindered structure to the six-membered ring, resulting in a monostable compound.

One example of P-perfluoroalkenyloxybenzaldehyde or P-perfluoroalkenyloxyphenylalkyl ketone used in the present invention, easily obtained by reaction of P-hydroxybenzaldehyde or P-hydroxyphenylalkyl ketone with hexafluoropropene oligomer . The details of this reaction can be found, for example, in
It is described in No. 7-56454.

2.2.4-) The dehydration reaction between dimethyl-1,3-bentanediol and P-perfluoroalkenyloxybenzaldehyde or P-perfluoroalkenyloxyphenylalkyl ketone is carried out using equivalent amounts of both and appropriate azeotropic dehydration. The reaction is preferably carried out using a solvent such as an aromatic solvent such as benzene under heating conditions in the presence of a conventional esterification catalyst such as p-)luenesulfonic acid, and the resulting system is taken out of the system. Reflux conditions when using aromatic solvents, e.g. 80°C in the case of benzene
It is preferable to carry out the reaction at a reaction time of 1 to 2 hours and a reaction time of about 90%.
The target compound can be obtained with a yield of % or more.

Although this dehydration reaction can be carried out without any solvent, azeotropic dehydration reaction using an aromatic solvent has mild reaction conditions and is easy to control, and the yield is extremely high, so it has excellent industrial productivity. There is.

The present invention will be explained in more detail with reference to Examples.

Example 1 2-Methyl-2-(4-perfluorononenyloxyphenyl)-4-isopropyl-5,5-dimethyl-1,
Synthesis of 3-dioxane P-hydroxyacetophenone 13 was added to a 500-flask equipped with a stirrer, thermometer-reflux condenser, and addition funnel.
．． 6 f (0.1 mol), N,N-dimethylformamide 80. ,t! and triethylamine 10r (0,
1 mol) was added. Hexafluoropropene trimer 5 was added under stirring while maintaining the temperature of the reaction system below 20°C.
0 f (0.11 mol) was added dropwise into the flask. After the dropwise addition was completed, the reaction was continued for about 2 hours, and the reaction mixture was poured into water, and the lower layer was separated and washed repeatedly with diluted hydrochloric acid, water, and 10% NaOH solution in this order.

The crude product was dried over anhydrous sodium carbonate and then distilled under reduced pressure to obtain compound A45y (yield: 80%). The physical properties of the obtained product were as follows.

Appearance: White solid Boiling point = 146-148℃ / 13 mrgHg Melting point: 4
2-44°C 2,2,4-trimethyl-1,3-bentanediol 1
4.6 y (0,1 mol) to compound A55 (0,1 mol)
Mol) (!:P-) 0.1y of luenesulfonic acid and 100% of benzene are charged into a flask equipped with a Dean-Stark distiller and a stirrer, and the resulting water is removed from the thread by azeotropy while 100% of benzene is added. The mixture was stirred at ℃ for 2 hours. After the reaction was completed, the mixture was neutralized and dried with anhydrous potassium carbonate, the solvent was distilled off, and the product was obtained by vacuum distillation. It was confirmed that the product showed a single peak in gas chromatography under the following conditions: The physical properties of the obtained product are shown in Table 1.

Example 2 2-(4'-perfluorononenyloxyphenyl)
Synthesis of -4-isopropyl-5,5-dimethyl-1,3-dioxane: Compound A of Example 1 except that 12.29 (0.1 mol) of P-hydroxybenzaldehyde was used in place of P-hydroxyacetophenone. Similarly to the synthesis of compound B
I got it. The physical properties of compound B were as follows.

Appearance: Colorless liquid Boiling point: 142-b Refractive index: 1.6628 (nD23°C) Compound of the present invention (
Synthesis of compound ■): Compound A was mixed with the above compound B53.6 f (0.1 mol)
A product was obtained in the same manner as in Example 1 except that .

Gas chromatography (same conditions as in Example 1) of the resulting product showed a single peak. Table 1 shows the physical properties of the product.

Table-1

[Brief explanation of drawings]

Figure 1 is the IR chart of compound ■, Figure 2 is the 'H-NMR chart of compound ■, and Figure 3 is the 19F-N of compound ■.
MR chart - Figure 4 is the IR chart of compound ■, Figure 5
The figure shows the 'H-NMR chart of compound ■, and Figure 6 shows the F-NMR chart of compound ■.
19F-NMR analysis δ, pm internal standard CCIF-C
The higher magnetic field side is indicated by a positive sign than the absorption line of Cl3F)
.

Claims (1)

[Scope of Claims] 2-(4'-perfluoroalkenyloxyphenyl)- represented by [In the formula, Rf represents a perfluoroalkenyl group having 2 to 20 carbon atoms, and - represents hydrogen or an alkyl group] 4-isopropyl-5゜5-dimethyl-1,
3-dioxane and its 2-alkyl substituted products. 2. 2. Reacting 4-trimethyl-1,3-bentanediol with P-perfluoroalkenyloxybenzaldehyde or P-perfluoroalkenyloxyphenylalkyl ketone □ [In the formula, Rf has 2 to 2 carbon atoms] 20 perfluoroalkenyl groups, k
represents hydrogen or an alkyl group]
4'-perfluoroalkenyloxyphenyl)-4-
A method for producing isopropyl-5°5-dimethyl-1,3-dioxane and its 2-alkyl substituted product. 3, 2, 2.4-) The second step of azeotropic dehydration of riftyl-1,3-bentanediol and P-perfluoroalkenyloxybenzaldehyde or P-perfluoroalkenyloxyphenylalkyl ketone in the presence of an organic solvent. Manufacturing method described.