JPS6293265A - Compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by the formula [R is -(CH2)m-; m is an integer 2-6; X is H or CH3]. USE:Useful as a monomer for organic high polymer liquied crystals and also monomer for photosensitive resins since it has photo-setting property and capable of imparting heat resistance by the photo-setting particularly in liquid crystal use. PREPARATION:p-Hydroxycinnamic acid is esterified with a hydroxyalkyl (meth) acrylate in the presence of a dehydrating agent, e.g. trifluoroacetic acid anhydride, at a low temperature to give an esterified substance, which is then reacted with p-cyanobenzoyl chloride in the presence of a dehydrochlorinating agent, e.g. trimethylamine, to afford the aimed compound expressed by the formula.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application and Prior Art] The present invention relates to a novel compound represented by the following general formula that has not been described in any literature.

[In the formula: R(CH2)-(m: an integer of 2 to 6)
Indicates knee H or -CH3. [Means for solving the problem] The gist of the present invention is a novel compound represented by the following general formula that has never been reported before.

[In the formula: R(CH14-(m: an integer of 2 to 6)
Indicates knee H or -CH. ] The compounds of the present invention include balananobenzoic acid chloride, buff hydroquine cinnamic acid and hydroxyalkyl pacrylic V-
It can be produced by dehydrochloric acid condensation of an esterified product of methacrylate or hydroxyacrylate.

Buff hydroquine cinnamic acid and hydroxyalkyl p (meth)
Esterification of acrylate is preferably carried out at a low temperature to prevent polymerization of (meth)acryloyl μ groups, and is preferably carried out at a temperature of 70° C. or lower.

In the esterification, it is preferable to use a dehydrating agent, and as the dehydrating agent, a dehydrating agent that is usually used in the same type of reaction can be used. A preferred example of this is trifluoroacetic anhydride. The amount of the dehydrating agent used is preferably from 1 to 4 times the amount of the (meth)acrylate, more preferably 2 times the amount of the (meth)acrylate.

The esterified product thus obtained is reacted with para-anobenzoic acid clophyte in the presence of a dehydrochlorination agent to obtain the compound of the present invention, but any dehydrochlorination agent that is normally used for similar purposes can be used. Preferred examples of the dehydrochlorination agent include ploidymethylamine, pyridine, and NN dimethylaniline. Since this combination reaction of dehydrochlorination is an exothermic reaction, it is preferable to suppress the heat generation at the beginning of the reaction as much as possible and to complete the reaction by heating at the end of the reaction.

If the value of m in the general formula of the present compound exceeds 6, it will be difficult to purify the esterified product of hydroxyacrylate or hydroxyacryl methacrylate and puffed hydroquine cinnamic acid, which are intermediate raw materials. This makes production difficult.

〔Example〕

The present invention will be explained in more detail below using Examples.

Example 1 Rose and Dorokingei skin acid 1.77N (280,9), hydroxyethyl methacrylate 1.77μ (21,99
) was dissolved in 1 t of dimethyl cellosolve, and then about 1.8 mo/I/(37
After reacting 0g) for 20 hours while being careful not to raise the solution temperature, 10 wt% of caustic soda was added.
Aqueous solution was added to neutralize. Add diethyl ether/l to this solution.
After adding 15 t of water and separating the aqueous layer, it was extracted three times with a saturated aqueous sodium bicarbonate solution and three times with distilled water. The ether/l/layer was dehydrated over anhydrous sodium sulfate overnight, and then evaporated in an evaporator t. - Diethyl ether μ and dimethyl cellosolve were removed to obtain 165 g of a crude reaction product. When this crude reaction product was examined using infrared absorption spectroscopy, high performance liquid chromatography, and proton nuclear magnetic resonance absorption spectroscopy, it was found that most of it was an ester of puffed hydroquine cinnamic acid and hydroxyethyl methacrylate. It was found that a small amount of unreacted hydroxymethacrylate was contained. Since the purity of the ester was relatively high, this crude reaction product was used as it was in the next reaction. That is, this crude reactant has approximately Q, 1 mo A72 Bfl and triethyl μ
Dissolve 20 g of amine in 200 ccK of dimethyl cellosolve and add 11 moles of balacyanobenzoic acid chloride (1 & 6,9
) was gradually added dropwise using a dropping funnel, followed by a reflux reaction for 8 hours. The precipitated triethylamine hydrochloride was separated by f, and f
Dimethyl cellosolve was removed from the solution using an evaporator, the remaining solid was dissolved in diethyl patep, and recrystallization from the solution was repeated twice to obtain the target compound. It was confirmed that the substance obtained here was a compound represented by the following chemical formula by elemental analysis, infrared absorption spectrum μ, and proton nuclear magnetic resonance spectrum μ. That is, the elemental analysis values of this substance (C: 6&5tll, H: 4.
4511°N: 57chi) is the above atomic weight 〇! ! H100
Calculated value of atomic weight fraction of 6N (C: 6 & 1%, H: 4
．． 7%.

N:! L5%).

The proton nuclear magnetic resonance spectra/L/ and infrared absorption spectra μ of this compound are shown in FIGS. 1 and 2. As shown in FIG. 1, each peak can be attributed to a proton in the corresponding molecular structure. Also, from Figure 2, λ220 cys
-', 1.595 cm-1 and 1625 cm-', absorptions attributed to the cyano group, vinyl A/i of cinnamic acid, and vinyl group of acryloyl group appear, respectively. These analysis results indicate that this substance is a compound represented by the above chemical formula.

The elemental analysis value of a compound synthesized in the same manner as in Example 1 except that hydroxyethyl acrylate of 7μ such as Example 2 and droxyethyl methacrylate (lK, etc.) was used was C:5Z2cI.
ISH24.11 N: 57 arrogance, chemical formula below (% formula %) Atomic formula of C22H1□0. Calculated value of atomic weight fraction of H C
: 67.5%, H: 4.3 Z, N: 16
% good < matched.

A compound in which R in formula (1) is -(aH, 4-(m: 3 to 6)) can also be obtained in the same manner as in Example 1.

〔Effect of the invention〕

The compound of the present invention can be used as a top layer for organic polymer liquid crystals, and since it has photocurability, it can be used as a monomer for photosensitive resins. Particularly in liquid crystal applications, nF#* properties can be imparted by photocuring.

[Brief explanation of drawings]

Figure 1 shows the proton nuclear magnetic resonance spectrum of the compound (E) synthesized in Example 1, and Figure 2 shows the infrared absorption spectrum μ.

Claims (1)

[Claims] A compound represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R: -(CH_2)___m- (m = an integer from 2 to 6) X: -H or -CH_3]