JPH05140012A - Fluorine-containing halogenated methyl derivative - Google Patents

Abstract

PURPOSE:To provide a new fluorine-containing methyl halide derivative useful as a raw material for giving excellent characteristics such as water-repelling and oil-repelling property, detackifying property, chemical resistance, flame retardancy, insulation property, etc., and also as a raw material for surfactants, medicines, agricultural chemicals, functional polymers, etc. CONSTITUTION:A compound of formula I (Rf is perfluoroalkenyl, perfluoroalkyl; Y is O, CH2; Ar is monocyclic-polycyclic aromatic group; X is halogen; n is an integer of 2-5), e.g. 3,5-dibromomethyl-perfluorononenyloxybenzene. The compound is obtained by reacting a fluorine-containing polymethylaryl compound of formula III with a reagent for selectively halogenating the allyl group, such as NBS. The compound can be reacted with e.g. a compound having a functional group such as phenolic OH, NH2 or SH to synthesize various compounds or polymers.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a novel fluorine-containing methyl halide derivative useful as a raw material for surfactants, pharmaceuticals, agricultural chemicals, fluorine-containing polymers and the like containing a perfluoroalkenyl group or a perfluoroalkyl group. Is provided.

[0002]

2. Description of the Related Art Introduction of a fluorocarbon into a molecule is
It is an important means for imparting properties such as excellent water and oil repellency, anti-adhesion properties, chemical resistance, flame retardancy, and insulation properties. In particular, the introduction of a perfluorocarbon group is important in order to further improve the properties of fluorocarbon,
Further, a perfluorocarbon compound having a polyfunctional group has been demanded so that it can be used in a wider range.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a fluorine-containing methyl halide having a polyfunctionality for introducing a perfluorocarbon, which can be used according to the required performance.

[0004]

That is, the present invention is based on the general formula (1):

[Chemical 2] (In the formula, Rf is a perfluoroalkenyl group, or
Indicates a perfluoroalkyl group. Y is, -O-, or, -CH ₂ - shows a. X represents halogen. n is
It represents an integer of 2 to 5. ) A fluorine-containing methyl halide derivative represented by In the general formula (1), Rf represents a perfluoroalkenyl group or a perfluoroalkyl group. Particularly, those having 6 to 12 carbon atoms are preferable. For example, a structure having the following formula can be considered. However, it is not limited to this.

[Chemical 3] Y is, -O-, or, -CH ₂ - shows a. Ar represents a monocyclic or polycyclic aromatic group. For example, benzene ring, naphthene ring, biphenyl and the like can be mentioned. X represents a halogen atom. Particularly, chlorine, bromine and iodine atoms are preferable. n shows the integer of 2-5, Preferably it is the integer of 2-3.

The general synthesis method of the general formula (1) is as follows:

[Chemical 4] (In the formula, Rf, Y, and n have the same meanings as described above), which is obtained by reacting a fluorine-containing polymethylaryl compound with an allyl-selective halogenating reagent such as NBS. .. However, this is an example of the synthesis method, and the present invention is not limited to this synthesis method.

The substance according to the present invention (general formula (1)) can be reacted with a compound having a functional group such as phenolic OH, NH2 and SH to synthesize various kinds of compounds and polymers.

[0007]

【Example】

Example 1 Synthesis of 3,5-dibromomethyl-perfluorononenyloxybenzene 5.52-Perfluorononenyloxymetaxylene 5.52
g (10 mmol), N-bromosuccinimide 3.74 g
A mixed solution of (21 mmol) and 50 ml of benzene is gradually heated and reacted under reflux for about 3 hours. After cooling, the precipitated solid was filtered off, benzene was concentrated under reduced pressure, and the resulting mixture was subjected to silica gel column chromatography (hexane-ether mobile phase) to give 3.21 g of the desired product (formula 3).
(45.2%) was obtained. The physical properties of the compound are shown in Table 1.

[Chemical 6] Example 2 Synthesis of 3,5-bis (bromomethyl) -α- (perfluoro-1 ′, 1 ″ -dimethylbutyl) toluene 11.9 g (5.0 × 10 5) 1-perfluorohexylmethyl-3,5-dimethylbenzene ^-2 mol), 19.6 g (1.1 x 10 ^-1 mol) of N-bromosuccinimide, 0.3 g (1.1 x 10 ^-3 mol) of benzoyl peroxide, and 150 ml of benzene were added. After completion of the reaction, the reaction solution was transferred to a separatory funnel, and 30 ml of an aqueous solution of about 5% sodium carbonate was added 3 times, 30 ml of an aqueous solution of about 5% sodium bicarbonate was added 3 times, and about 30% of an aqueous saturated sodium chloride solution was added. The organic layer was dried with anhydrous sodium sulfate, and then benzene was removed under reduced pressure to obtain 26.7 g of a crude product (yield 89%). Phase silica gel column Intended product Mato chromatography physical properties of (Equation 4) 9.3 g was obtained. Said purpose thereof are shown in Table 2.

[Chemical 7]

[0008]

INDUSTRIAL APPLICABILITY The substance according to the present invention is used as a raw material for imparting properties such as water and oil repellency, anti-adhesion, chemical resistance and flame retardancy, for example, surfactants, pharmaceuticals, agricultural chemicals, or functional polymers. It is useful as a raw material.

[Chemical 5]

Claims (1)

[Claims] 1. General formula (1): (In the formula, Rf is a perfluoroalkenyl group, or
Indicates a perfluoroalkyl group. Y is, -O-, or, -CH ₂ - shows a. Ar represents a monocyclic or polycyclic aromatic group. X represents a halogen atom. n is 2 to
Represents an integer of 5. ) A fluorine-containing methyl halide derivative represented by