JP2002241348A - New compound and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new ethylenically unsaturated compound containing an antioxidant residue and to provide a method for producing the same. SOLUTION: This new compound is represented by the chemical formula (R is a hydrogen atom or a methyl group). This method for producing the compound is characterized in that 5,6,5',6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'- spiroindane is reacted with acrylic acid chloride or methacrylic acid chloride in the presence of a base.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel compound and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Many spiroindanes are known,
Some have been used as antioxidants.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel compound, and in particular, to provide a novel ethylenically unsaturated compound containing an antioxidant residue and a method for producing the same.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a novel compound, and its chemical structural formula is as follows.

Embedded image In the formula, R represents a hydrogen atom or a methyl group. In addition, the production method is based on 5,6,5 ′, 6′-tetrahydroxy-
A process for producing the above compound, which comprises reacting 3,3,3 ′, 3′-tetramethyl-1,1′-spiroindane with acrylic acid chloride or methacrylic acid chloride in the presence of a base.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The novel compounds of the present invention and their analogs are 5,6,5 ', 6'-tetrahydroxy-3,
It is synthesized by reacting 3,3 ′, 3′-tetramethyl-1,1′-spiroindane with an ethylenically unsaturated carboxylic acid or an active derivative thereof, for example, an acid halide. When reacting an ethylenically unsaturated carboxylic acid, it is preferable to coexist a dehydrating agent. When reacting an acid halide, it is preferable to coexist a base such as an amine.

The ethylenically unsaturated carboxylic acid which can be used in the production of the compound of the present invention is not particularly limited. For example, ethylenically unsaturated monocarboxylic acid monomers such as acrylic acid and methacrylic acid; And ethylenically unsaturated polycarboxylic acid monomers such as fumaric acid and butenetricarboxylic acid; partial esters of ethylenically unsaturated polycarboxylic acids such as monobutyl fumarate, monobutyl maleate and mono-2-hydroxypropyl maleate Monomers; and the like. Examples of the acid halide include acid chlorides, acid bromides and acid iodides of the above-mentioned ethylenically unsaturated acids. The acid chloride can be preferably used because it has an appropriate reactivity. Ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid are preferred, methacrylic acid or acrylic acid is more preferred, and their acid chlorides are particularly preferred.

The compound of the present invention is synthesized by the following reaction. The reaction formula using methacrylic chloride is shown below.

Embedded image

The amount of the ethylenically unsaturated carboxylic acid or its acid halide to be used can be stoichiometric or an excess of several tens of mol% based on hydroxyspiroindane. During the reaction, the carboxylic acid component is preferably added dropwise to the reaction system. When a base is allowed to coexist, it is preferable to use an excess of the stoichiometric amount to capture the hydrogen halide generated by the reaction. Tertiary amines such as pyridine and triethylamine are preferably used as the base.

In the reaction, an inert solvent is preferably used, and ethers such as ethyl ether and THF can be preferably used. The amount used is not particularly limited, but per mole of hydroxyspiroindane as a raw material,
0.2 to 2 kg. In order to prevent undesirable addition polymerization of the ethylenically unsaturated carboxylic acid or its active derivative during the reaction, it is preferable to use a polymerization inhibitor such as hydroquinone in combination.

The reaction temperature for producing the compound of the present invention can be arbitrarily selected from the range of 0 ° C. to 80 ° C. A temperature of 25 ° C to 70 ° C is preferred because a suitable reaction rate is obtained. Since the reaction time depends on the rate of addition of methacrylic acid chloride and the like, it cannot be said unconditionally.
Ten hours are common.

As a post-treatment after the reaction, a mixture of water and an organic solvent insoluble in water is added to the reaction mixture, and the target substance is extracted into the organic solvent. Then, the organic solvent is distilled off. The target substance can be crystallized from the residue according to a conventional method.

The compound of the present invention can be used as an antioxidant, and can be used in combination with a composition containing an ethylenically unsaturated compound to produce a resin composition having an antioxidant function.

[0013]

EXAMPLES (Example 1) Raw material 5,6,5 ', 6'-tetrahydroxy-3,3,3', 3'-tetramethyl-
192.7 g of 1,1'-spiroindane (0.556
Mol), THF 1156.2 g, polymerization inhibitor 38.5 m
g and triethylamine 343.7 g were charged into a reaction vessel. 295.9 g of methacrylic acid chloride was added dropwise thereto over about 2 hours while controlling the internal temperature at 30 to 63 ° C., and the reaction was carried out for 2 hours. To this reaction solution was added toluene 10
0.7 g and 302.4 g of water were added, extraction and washing were performed, and the aqueous layer was discarded. Further, the organic layer was washed with 100 g of aqueous sodium bicarbonate and then with 100 g of water. Thereafter, the toluene was concentrated under reduced pressure to obtain an extract. This extract was dissolved in a mixed solution of toluene / n-hexane, cooled, crystallized, filtered and dried to obtain 190 g (yield: 54.8%) of the target compound in the reaction formula shown in Chemical formula 3.
The characteristic values are shown below. Melting point: 194 ° C. Peak value of NMR spectrum (in CDCl ₃ ): 1.3
0 ppm (6H, s), 1.35 ppm (6H, s),
1.95 ppm (6H, s), 2.00 ppm (6H, s)
s), 2.30 ppm (4H, m), 5.65 ppm
(2H, s), 5.70 ppm (2H, s), 6.20
ppm (2H, s), 6.25 ppm (2H, s),
6.70 ppm (2H, s), 7.05 ppm (2H, s)
s). The NMR spectrum is shown in FIG.

[Brief description of the drawings]

FIG. 1 shows NMR of a novel compound (R = methyl group) of the present invention.
The spectrum is shown.

Claims (2)

[Claims] 1. A novel compound represented by the following chemical formula. Embedded image In the formula, R represents a hydrogen atom or a methyl group. (2) 5,6,5 ', 6'-tetrahydroxy-
The method for producing a compound according to claim 1, wherein 3,3,3 ', 3'-tetramethyl-1,1'-spiroindane is reacted with acrylic acid chloride or methacrylic acid chloride in the presence of a base.