JPH05279320A - Bisphenol compound - Google Patents

Abstract

PURPOSE:To provide the subject compound good in developed color deepness, chemical resistance and preservability as a developer for recording materials, also serving as a new raw material for polymers. CONSTITUTION:The objective bisphenol compound of formula I, which can be obtained, for example, by the following process: 4,4'-dihydroxydiphenylsulfone is made to react with 3-chloro-2-methylpropene in a solvent in the presence of a catalyst such as sodium hydroxide or potassium carbonate to form a diether modification, which is, in turn, put to Claisen rearrangement under a nitrogen gas flow at 150-250 deg.C for 15-100hr into a compound of formula II, which is then reduced in a protic solvent, nonpolar solvent, or mixed solvent thereof using a Raney nickel under hydrogen gas pressurization at 20-70 deg.C.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a recording material using an electron-donating colorless dye and an electron-accepting compound, for example, a pressure-sensitive recording material, an electron-accepting compound or a coupler for a heat-sensitive recording material,
The present invention relates to a bisphenol compound useful as a polymer material and the like, and a bisphenol compound useful as a synthetic intermediate thereof.

[0002]

BACKGROUND OF THE INVENTION Various phenolic compounds are known as electron-accepting compounds for pressure-sensitive recording materials and heat-sensitive recording materials. In all of them, color density, color sensitivity, unprinted area storability, and printed area storability ( It has some drawbacks in light resistance, chemical resistance, etc.). For example, when 4-isopropoxy-4'-hydroxydiphenyl sulfone disclosed in Japanese Examined Patent Publication (Kokoku) No. 3-54655 is used as a thermal recording paper, it exhibits high color density and sensitivity, but must be written with a marker or a highlighter pen. As a result, the unprinted part was colored, the printed image disappeared, and the chemical resistance was insufficient.

Further, when bis- (3-phenyl-4-hydroxyphenyl) sulfone disclosed in JP-A-2-266981 is used for a thermal recording paper, the color developing sensitivity is low,
Although the image was not erased by writing with a marker or a highlighter, the unprinted part was colored, and when a hand cream or the like adhered, the image was erased immediately, resulting in insufficient chemical resistance. Although the bisphenol compound proposed here is extremely useful as a raw material for polysulfone, it has hardly been studied. It is particularly effective as a raw material for polyether sulfone, polyurethane sulfone, polycarbonate, polyester and the like.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a novel bisphenol compound which, in an acid-base color-developing system, simultaneously satisfies color density, color sensitivity, unprinted part storage property, printed part storage property and the like. is there.

[0005]

Means for Solving the Problems The above problems have been achieved by a bisphenol compound represented by the following chemical formula (1). Chemical formula (1)

[0006]

[Chemical 3]

The compound of the present invention can be synthesized according to various synthetic routes via the compound of the chemical formula (2). For example, 4,4'-dihydroxydiphenyl sulfone and 3-
Chloro-2-methylpropene is reacted in a solvent to obtain a diether body. As the solvent, water, a protic solvent such as alcohol, an aprotic solvent such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, a polar solvent such as acetonitrile, ethyl acetate, acetone and toluene, a non-solvent such as hexane, benzene and ether. Polar solvent,
A halogen-containing solvent such as dichloromethane or chloroform, or a mixed solvent thereof is effective. It is useful to use a catalyst together, and sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and the like are preferable. Usually, the reaction is carried out at 20 to 150 ° C. for 1 to 24 hours. In this way, an ether body is obtained. Then, the obtained diether body under a nitrogen stream,
The Claisen rearrangement reaction is performed at 150 to 250 ° C. for 15 to 100 hours, cooled, and then separated and purified by silica gel column chromatography. Thus, the chemical formula (4)
A compound represented by Next, reduction is carried out at 20 to 70 ° C. under hydrogen pressure with Raney nickel in a protic solvent such as alcohol, a non-polar solvent such as ethyl acetate, toluene, or a mixed solvent thereof, and is represented by the chemical formula (1). To obtain a bisphenol compound. Also, starting material is 4,
From 4'-dihydroxydiphenyl sulfone, 4,4 '
-It is also possible to change to thiophenol and subsequently obtain the target product through an oxidation step.

Chemical formula (4)

[0009]

[Chemical 4]

Examples are shown below, but the present invention is not limited thereto.

[0011]

【Example】

Example 1 Synthesis of compound represented by chemical formula (2) 0.2 mol of 4,4'-hydroxydiphenyl sulfone, 0.4 mol of 3-chloro-2-methylpropene and 0.41 mol of potassium carbonate were added. N, N-dimethylacetamide 30
It was weighed in 0 cc and then stirred at 80 ° C. for 4 hours. The reaction solution is poured into 2 liters of water, and the obtained crystals are filtered and washed well with water. The crystals were washed with methanol to obtain a compound having a melting point of 117 ° C. The compound obtained by etherification is stirred at 170 ° C. for 24 hours in a nitrogen atmosphere. It was cooled to room temperature and isolated by column chromatography using silica gel with hexane / ethyl acetate as a developing solvent to obtain an oily target product. The NMR spectrum is shown below. (Solvent, deuterated chloroform) (δ, ppm) 1.
68 (s) 6H, 3.35 (s) 4H, 4.68 (s)
2H, 4.85 (s) 2H, 6.88-6.95 (d)
2H, 7.58 to 7.67 (m) 4H As a by-product, a melting point of 7 represented by the chemical formula (5)
A compound at 6 ° C. was obtained.

Chemical formula (5)

[0014]

[Chemical 5]

Example 2 Synthesis of Compound Represented by Chemical Formula (1) The compound obtained in Example 1 and Raney nickel [Kawaken Fine Chemical Co. (Raray NDNT-90)] catalyst amount were weighed in 200 cc of ethanol, 5 under hydrogen pressure
Stir at 0 ° C. for 5 hours. Raney nickel in the reaction solution was carefully filtered, the furnace solution was concentrated by a rotary evaporator, and was isolated by column chromatography using silica gel with hexane / ethyl acetate as a developing solvent to give a melting point of 76.
The desired product at ℃ was obtained. The NMR spectrum is shown below.
(Solvent, deuterated chloroform) (δ, ppm) 0.80
0.90 (d) 12H, 1.95-2.00 (m) 2
H, 2.45 to 2.55 (d) 4H, 6.80 to 6.9
5 (d) 2H, 7.48-7.60 (m) 4H

Claims (2)

[Claims] 1. A bisphenol compound represented by the chemical formula (1): [Chemical formula (1)] 2. A bisphenol compound represented by the chemical formula (2): [Chemical formula (2)]