JP2620290B2 - Method for producing aryl ether compound having silyloxy group - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing an adduct obtained by reacting a silyl ether with an epoxy compound. More specifically, the present invention relates to a method for producing a silyloxy group-containing aryl ether compound obtained by reacting a monofunctional or bifunctional aryl or arylenesilyl ether with a monofunctional or bifunctional epoxide using a catalyst.

[Problems to be solved by conventional technology and invention]

Epoxides have high reactivity and have been regarded as important as synthetic intermediates. Among them, since a silyloxy group is useful as a protecting group, catalysts have been studied for the reaction of various silyl compounds with epoxides.

For example, 0-silyl azide hydrin has been obtained from silyl azide and epoxide using a metal alkoxide as a catalyst [C. Brandy et al., Tetrahedron Lett., 24 , 4189].
(1983)].

Further, silyl halide is added to an epoxide using triphenylphosphine as a catalyst to give 0-silylhalohydrin [GC Andrews et al., Tetrahedron Lett.
t., 22 , 3803 (1981)].

After the addition of silyl triflate to the epoxide in the presence of a base, the acid is eliminated to give 0-silyl allyl alcohol [Murata et al., J. Am. Chem. Soc. 101, 2738.
(1979)].

Furthermore, it is known that a similar adduct is obtained from silyl selenide and epoxide using a ZnI ₂ catalyst [N. Miyoshi et. Al., Chem. Lett., 909 (1979)].

However, there is no example in which an adduct is obtained from a silyl ether and an epoxide as shown in the present invention.

Therefore, of course, there is no application to the production of epoxy resin.

In order to separately synthesize the adduct obtained in the present invention, an aryl ether is obtained from the corresponding halohydrin and an aryl oxide, and then a silyl halide is acted on, or an epoxide and a phenol are acted on in the presence of a base or a quaternary ammonium salt, Further, a silylation method can be considered, but side reactions such as halohydrin cyclization reaction and epoxide polymerization are inevitable.

Further, in order to obtain the epoxy resin obtained by the present invention by a conventional method, for example, a method in which a free hydroxyl group of an epibis epoxy resin is silylated with a silyl halide can be considered, but attack of a halide on the epoxy group, polymerization of the epoxy group is considered. Is inevitable.

[Means for solving the problem]

As a result of earnest research, the inventor did not involve side reactions,
The present inventors have found a method for quantitatively obtaining an adduct under mild conditions, and have reached the present invention.

That is, the present invention relates to an aryl or arylene sil ether represented by the following general formula: Wherein R ¹ is an alkyl group or an aryl group, R ² is an alkyl group, an aryl group, an aryloxy group or an alkoxy group, Ar is an aryl group or a group represented by the following general formula, (Wherein R ¹ and R ² are the same as in the general formula, X is a hydrogen atom or a halogen atom, W is —NH—, —O—, —CH ₂ —, Or -SO ₂ -group)] wherein an aryl compound having a silyloxy group is subjected to an addition reaction with an epoxy compound having at least one terminal epoxy group in one molecule in the presence of an inorganic fluoride catalyst. It concerns the manufacturing method.

The compounds represented by the general formula of the present invention include the following.

Among the compounds represented by the general formula of the present invention, those having a trimethylsilyl group or a dimethylsilyl group are particularly preferably trimethylsilyl chloride or dimethylsilyl in the presence of a corresponding phenol or naphthol and a small excess of a base such as hexamethyldisilazane or pyridine. It is easily obtained by reacting with dichloride.

Examples of the epoxy compound having at least one terminal epoxy group in one molecule used in the present invention include conventionally known aromatic epoxy compounds and aliphatic epoxy compounds.

Preferred as such an aromatic epoxy compound is a polyglycidyl ether of a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof, such as biphenol A or an alkylene oxide adduct thereof and epichlorohydrin. And glycidyl ethers produced by the reaction with

Further preferable as the aliphatic epoxy compound is a pogiglycidyl ether of an aliphatic equivalent alcohol or an alkylene oxide adduct thereof, a polyglycidyl ester of an aliphatic long-chain polybasic acid, a homopolymer of glycidyl acrylate or glycidyl methacrylate, a copolymer, and the like. Representative examples are diglycidyl ether of 1,4-butanediol, diglycidyl ether of 1,6-hexanediol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, ethylene glycol, propylene glycol, glycerin and the like. One or two aliphatic polyhydric alcohols
Examples thereof include polyglycidyl ethers of polyether polyols obtained by adding at least one kind of alkylene oxide, and diglycidyl esters of aliphatic long-chain dibasic acids. Furthermore, monoglycidyl ethers of higher aliphatic alcohols, phenol, cresol, butylphenol or monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxides to these, glycidyl esters of higher fatty acids, epoxidized soybean oil, butyl epoxy stearate Octyl epoxy stearate, epoxidized linseed oil, epoxidized polybutadiene, and the like.

The addition reaction of the present invention is performed in the presence of an inorganic fluoride catalyst. Such catalysts include LiF, KF, NaF, CsF, RbF.

In the addition reaction of the present invention, if a salt such as ZnI ₂ is used as a catalyst, polymerization of an epoxy group takes precedence. Similar results are obtained with trimethylsilyl triflate, tetraalkylammonium fluoride and the like.

The reaction of the present invention can be carried out at 50 ° C to 200 ° C in the absence of a solvent or in a solvent such as an aromatic hydrocarbon, an alkyl ether, an alicyclic ether, an alkyl amide, or an alkyl sulfoxide. Preferably, in the present addition reaction, when the catalyst is heated to 100 ° C. to 150 ° C. using a catalytic amount of 0.1 to 10 mol%, preferably 0.5 to 5 mol% with respect to the silyl ether, a high yield can be obtained in the absence of a solvent. An adduct is obtained. The reaction proceeds sufficiently in 30 minutes to 3 hours, preferably 1 hour.
The higher the basicity of the phenol, the raw material of the arylsilyl ether, the higher the reactivity, and a normal adduct to the epoxide can be obtained more selectively.
It was speculated that cesium phenoxide was formed once, and that the reaction proceeded by phenoxide attack on the epoxide.

 An example of the progress of the reaction in the present invention is as follows.

[Effect of the Invention] According to the present invention, an adduct in which one of adjacent diols having various substituents is arylated and the other is silylated is obtained. Moreover, a silyl ether of a secondary alcohol is mainly obtained. These adducts are stable compounds in an alkaline or neutral atmosphere, and can be applied as they are to surfactants and defoamers. On the other hand, it is also important as a synthetic intermediate. When the present adduct is hydrolyzed with an acid, a secondary alcohol having various substituents and an aryloxy group at the β-position is obtained.

In addition, a ketone having various substituents and an aryloxy group at the β-position can be obtained in one step by Jones oxidation.

Further, as an application, an epoxy resin having a silyloxy group in a side chain can be obtained by a simple method.

Alkyl silyl ethers show little activity against addition reactions to epoxides. That is, the addition product, the silyl ether of the secondary alcohol, no longer reacts with the epoxide. By utilizing this functional group selectivity, an epoxy resin having a silyl ether group in the molecule can be produced as an application of the present invention. That is, a difunctional arylsilyl ether and a small excess, preferably 1.5 to 2.5 equivalents of a usual liquid epoxy resin are used without solvent in an amount of 0.1 to 10 mol%, preferably 0.5 to 5 mol%, based on the silyl ether. When heated to 100 ° C. to 150 ° C. using a catalytic amount of CsF, the addition reaction proceeds efficiently, and an epoxy resin having a silyloxy group in a side chain is obtained. Further, the reaction proceeds even in a solvent such as xylene, and an epoxy resin having a narrow molecular weight distribution can be obtained.

This is an epoxy resin having high solubility in organic solvents and excellent workability. High compatibility with siloxane polymers. Furthermore, it shows high adhesiveness to glass, metal and the like. Further, there is no free hydroxyl group found in the conventional epoxy resin, and it has excellent moisture resistance.

From these points, it is useful as a new type of epoxy resin, and its properties can be controlled by mixing it with a conventional epoxy resin.

〔Example〕

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Example 1 0.25 g (1 mmol) of CsF was weighed and dried in a reaction vessel equipped with a two-way cock, and then 8.3 g (0.05 mol) of phenyltrimethylsilyl ether and 7.5 g (0.05 mol) of phenylglycidyl ether were added under a nitrogen stream. In addition, lightly deaerate and seal. Heat the contents at 130 ° C. for 1 hour with good stirring. After the reaction, the product was purified with a silica gel column using chloroform as a developing solution to obtain 12.9 g (0.04 mol) of phenyl-2-trimethylsiloxy-3-phenoxy-propyl ether.

bp .: 150 to 160 ° C./0.45 mmHg (Cougalow distillation) IR: 1240,1280 cm ⁻¹ (ether) ¹ H NMR (CCl ₄ ): 0.15 (s, 9H, OSiCH ₃ ), 3.90 (m, 4H, PhOC)
_{H 2), 4.30 (m,} 1H, SiOCH -), 6.7~7.4ppm (m, 10H, C
^{_{6 H 5) 13 C NMR (}} CDCl 3): 0.0 (OSiCH 3), 69.16 (PhOCH 2), 69.
55 (SiOCH), 114.19,120.57,129.15,158.34ppm a (C ₆ H ₅₎ Example 2 to 7 p-substituted phenyl-trimethylsilyl ether and phenyl glycidyl ether, and reacted in the same manner as in Example 1 CsF as a catalyst, Purification on a silica gel column gave the corresponding p-substituted phenyl-2-trimethylsiloxy-3-
Phenoxypropyl ether was obtained in high yield. Table 1 shows the results.

Example 8 Dimethyldiphenoxysilane and phenylglycidyl ether were reacted in the same manner as in Example 1 using CsF as a catalyst, and dimethylbis [2-phenoxy-1- (phenoxymethyl) was obtained in a yield of 99% ( ¹ H NMR). [Ethoxy] silane was obtained. _{^{1 H NMR (CCl 4):}} 0.30 (s, 6H, SiCH 3), 4.00 (m, 8H, OC
_{H 2), 4.50 (m,} 2H, CH), 6.7~7.3 (m, 20H, C 6 H 5) Example 9 Bisphenol A bis (trimethylsilyl ether)
11.2 g (0.03 mol), bisphenol A diglycidyl ether (epoxy equivalent: 337.3) 20.2 g (0.06 mol), CsF
After reacting 0.114 g (0.75 mmol) at 130 ° C. for 1 hour in the same manner as in Example 1, the mixture was dissolved in chloroform, CsF was separated by filtration, and the solvent was removed. An epoxy resin having a siloxy group in the side chain was obtained. The residual ratio of epoxy to the starting silyl ether was 1.0 equivalent, the number average molecular weight in terms of polystyrene was 1970, and the molecular weight distribution was 1.64 (all excluding the starting material).

IR: 1245,845cm ^-1 (-CO-Si) Example 10 The same reaction as in Example 9 was carried out in a xylene solvent (180 ml).
0.182 g (1.2 mmol) of sF was heated at 140 ° C. for 2 hours. As a result, the conversion to trimethylsiloxy residue was 64%, the epoxy residual ratio was 1.03 equivalent, the number average molecular weight in terms of polystyrene was 7
An epoxy resin having a trimethylsiloxy group on the side chain having a molecular weight distribution of 1.16 was obtained.

Example 11 Bisphenol A bis (trimethylsilyl ether)
11.2 g (0.03 mol), 19.8 g (0.06 mol) of hexanediol diglycidyl ether (epoxy equivalent: 165), CsF0.
114 g (0.75 mmol) were reacted at 140 ° C. for 1 hour in the same manner as in Example 9 to obtain an epoxy resin having a conversion of silyl ether of 87% and a residual ratio of epoxy of 1.3 equivalents and having a trimethylsiloxy group in a side chain. Was. Polystyrene reduced number average molecular weight: 1447, molecular weight distribution: 1.62.

Claims (1)

(57) [Claims] An aryl or arylene silyl ether represented by the following general formula: Wherein R ¹ is an alkyl group or an aryl group, R ² is an alkyl group, an aryl group, an aryloxy group or an alkoxy group, Ar is an aryl group or a group represented by the following general formula, (Wherein R ¹ and R ² are the same as in the general formula, X is a hydrogen atom or a halogen atom, W is —NH—, —O—, —CH ₂ —, Or -SO ₂ -group)] wherein an aryl compound having a silyloxy group is subjected to an addition reaction with an epoxy compound having at least one terminal epoxy group in one molecule in the presence of an inorganic fluoride catalyst. Manufacturing method.